Analytica Chimica Acta 405 (2000) 3142

Fluorimetric determination of dissolved aluminium in natural waters after liquidliquid extraction into n-hexanol
J. Zhang a, , H. Xu b , J.L. Ren a
a

Department of Marine Chemistry, The Ocean University of Qingdao, 5 Yushan Road, Qingdao 266003, PR China b Department of Applied Chemistry, Yantai University, Yantai 264005, PR China Received 8 February 1999; received in revised form 24 August 1999; accepted 3 September 1999

Abstract A sensitive and selective extraction-uorimetric method for the determination of trace amount of dissolved aluminium in natural waters is developed in this study. Aluminiumlumogallion complex (AlLMG) is extracted into n-hexanol, and the uorescence can be enhanced substantially up to 20-fold. Compared to other publications in the literature, the method reported here is free from matrix effects, and the interference from iron and uoride has been minimised successfully by Be2+ and o-phenanthroline, respectively. The detection limit of dissolved Al is 0.25 nM, which is one order of magnitude lower than the traditional uorescence techniques, with a precision of 5% at an Al level of 40 nM and 6.7% at an Al level of 1.0 nM in routine analyses. The inter-calibration with electro-thermal atomic absorption spectrometry (ETAAS) technique for a variety of natural water samples shows a difference of 510%. The analysis of international SRM 1643C reference material by the method developed here provides a result consistent with the certied value. The successful inter-laboratory calibration practice demonstrates again the merit of present analytical procedure for the determination of Al in environmental and marine sciences. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Fluorimetric determination; Dissolved aluminium; Liquidliquid extraction; n-Hexanol

1. Introduction The traditional uorimetric determination of dissolved Al by the complex with lumogallion (LMG) is based on the exhibition of AlLMG compound (AlLMG) at an excitation wavelength of 465 nm and an emission wavelength of 555 nm. The method was rst proposed by Nishikawa and co-workers in 1967 and 1968 and later modied by Hydes and Liss in 1976 [13]. The method has been widely applied for
Corresponding author. Tel.: +86-532-2032005; fax: +86-5322963005. E-mail address: zhangj@lib.ouqd.edu.cn (J. Zhang).

the analysis of dissolved Al in aquatic environments in the last three decades [47]. However, the traditional LMG method exhibits two important shortcomings. First, the determination is biased by ionic interference like F and Fe3+ ; hence, for the application to natural water samples (e.g. estuarine water), an increment calibration procedure has to be used, recognising that the standard addition procedure may not eliminate the spectrum interference [8]. Second, though the detection limit of Al by the LMG method was reported to be as low as nano-molar level (e.g. 3 nM), based on the standard deviation of repeated determinations, the analysis of real samples is deteriorated by the reagent blanks and a reduction in the signal to noise

0003-2670/00/$ see front matter 2000 Elsevier Science B.V. All rights reserved. PII: S 0 0 0 3 - 2 6 7 0 ( 9 9 ) 0 0 6 9 0 - X

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(background) ratio of instrument, which leads to the lowest concentration reached being often at tens of nano-molar level for routine analyses [9,10]. This detection level is much higher than those reported by other techniques, for example, liquidliquid extraction and electrothermal atomic absorption spectrometry (ETAAS) in combination (0.09 nmol kg1 ) [11]. Resing and Measures [12] recently improved the uorimetric method by employing the ow injection analysis (FIA) technique in combination with in-line pre-concentration of Al on to a column of resin-immobilised 8-hydroxyquinoline; the uorescence of AlLMG is further enhanced by a micelle-forming detergent Brij-35; the reported detection limit is 0.15 nM. The laboratory test with 8-hydroxyquinoline extraction of Al in estuarine and seawater samples indicates, however, a rather low recovery compared to standard addition, which is probably due to the fact that 8-hydroxyquinoline may not be able to release Al3+ combined with F (e.g. AlFx (x 3) (x: 16)) [9]. The present work is aimed at developing an analytical scheme that is sensitive and selective for the determination of dissolved Al in various matrices, with Fe3+ and F over a wide concentration range. Since the FIA and continuous analysis (CA) techniques are not available, the method was substantiated manually in the laboratory with help of a class 100 clean bench. The traditional LMG method was combined with pre-concentration and separation by liquidliquid extraction into n-hexanol. The optimal conditions for operation and potential interference from common major and trace species were carefully evaluated. This has resulted in a method that allows the precise determination of Al in fresh water (river, rain and lake), brackish water (e.g. estuary) and seawater. The robust character of the method was also examined by the analysis of international SRM 1643C standard and through inter-laboratory calibrations.

wavelength is set to 595 nm for aqueous solution and 580 nm for organic extraction, respectively, for the reasons discussed later. The spectrum slit is xed at 5 nm for both excitation and emission wavelengths. Other instrumental parameters include the response time of 2 s with low photomultiplier gain and emission lter open. For the inter-calibration of Al determination with ETAAS, the PerkinElmer 1100B and PerkinElmer 4100ZL instruments are used.

2.2. Reagents All experiments are performed with high-purity grade chemicals and solvents. When necessary, HCl is puried by sub-boiling distillation. Double distilled and Milli-Q waters are used in the experiments. All plastic-ware is made of polyethylene unless mentioned otherwise. Bottles and laboratory wares are washed with hot detergent, followed by thoroughly rinsing with doubled distilled water, and they are immersed in HCl (1 : 4 v/v) for 1 week and rinsed again with Milli-Q water before use. The stock solution of Al (50 mM of Al at pH = 1) is prepared by dissolving 23.7184 g of aluminium(III) potassium sulphate dodecahydrate (KAl(SO4 )2 12H2 O) in HCl, and then diluted to 1000 ml. This standard solution can be stored in plastic bottle at 04 C in dark for several months. Working standards containing 0.5 mM of Al or less are prepared daily by appropriate dilution of stock solution with Milli-Q water. The LMG solution is prepared by dissolving 20 mg of LMG (4-chloro-6-[(2,4-dihydroxyphenyl)azo]-1hydroxybenzene-2-sulfonic acid) in 100 ml of Milli-Q water in a 250 ml Teon bottle. The solution has been found to be stable for 1 month if stored in dark at low temperature (04 C). A buffer solution of pH = 5.0 is prepared by mixing 32.0 g of sodium acetate (NaAc) with 12 ml of acetic acid (HAc), then diluted to 100 ml in a Teon bottle. The trace amount of Al in the buffer solution is removed by complexing with LMG and extraction with n-hexanol. The solution is stable for 1 month, if stored in dark at low temperature (04 C). The Be2+ solution (50 mM) is prepared by dissolving 0.8857 g of BeSO4 4H2 O in 100 ml of Milli-Q water, and stored at 04 C. The solution of

2. Experimental 2.1. Apparatus A HITACHI-850 Spectrouorimeter is used for the measurements of Al in this study. The excitation wavelength is set to 500 nm, and the emission

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33

o-phenanthroline (15 mM) is prepared by dissolving 0.3 g of o-phenanthroline (C12 H8 N2 H2 O) in 100 ml of Milli-Q water, and stored at 04 C before use. 2.3. Recommend procedure In 100 ml of ltered and acidied water sample (pH 2), an amount of extra-pure NH3 H2 O is added to adjust sample to pH 4, followed by adding 55 l of o-phenanthroline solution (i.e. 8 M) and 300 l of Be2+ solution (i.e. 150 M). Add 1.0 ml of NaAcHAc buffer solution to the sample, and the pH of sample will reach 5.0 0.1. 1.0 ml of LMG is added to the sample (i.e. 2 mg l1 ), and sample is heated at 80 C for 90 min or at 25 C for 120 min. The sample is transferred to a 250 ml Teon separatory funnel, AlLMG in water sample is extracted four times, each with 5 ml of n-hexanol, and the organic fractions are combined after extraction. The uorescence of Al in organic extracts is measured at an excitation wavelength of 500 nm and an emission wavelength of 580 nm.

Table 1 Comparison of the efciency of extraction of AlLMG into various organic solventsa Solution Chloroform Cyclo-hexane Tetrachloromethane Freon-113 Benzacohol Iso-pentanol Cyclo-hexanol n-Hexanol Fluorescence 0.025 0.002 0.005 0.001 0.002 0.001 0.001 0.001 4.420 0.020 8.772 0.030 9.765 0.040 8.305 0.030 Extraction (%) 4.4 0.4 0 0 0 21.1 0.1 57.4 0.3 80.7 0.3 76.8 0.3

a The extractions are carried out at pH = 5 in 100 ml of Milli-Q, with an Al concentration of 0.9 M. Other experiment conditions: LMG 2 mg l1 ; extraction 10 ml 1 of solvent. The uorescence of 0.9 M Al in Milli-Q is 0.486 0.005; the relative deviation is 1.0%. The extraction efciency is calculated by the difference of Al in aqueous solution before and after extraction.

3. Results and discussion 3.1. Optimisation of the method 3.1.1. Selection of extraction solution Table 1 shows the comparison of the efciency of extraction of Al by various organic solvents at pH = 5, at which the maximal uorescence of AlLMG was observed in aqueous solution. LMG contains three hydroxyls, which may complex with Al in aqueous solution, and AlLMG illustrates a higher afnity with polar organic solvents than non-polar solutions. In Table 1, the weak and non-polar solvents, like cyclo-hexane, carbon tetrachloride, and Freon-113, are unable to extract AlLMG complex, whereas polar solvents, like iso-pentanol, cyclo-hexanol, and n-hexanol, illustrate a signicant ability for removing AlLMG from aqueous solution. Among the various organic solvents in Table 1, cyclo-hexanol shows the highest extraction recovery, reaching 81%. However, cyclo-hexanol has a rather high viscosity and melting point (25.2 C), hence is liable to congeal at room temperature, which limits the application of cyclo-hexanol extraction in

routine analysis. Iso-pentanol has a strong and unpleasant smell, and shows higher solubility in water than cyclo-hexanol and n-hexanol, which reduces the extraction recovery of AlLMG. Compared to other organic solvents, n-hexanol demonstrates a fairly good extraction for AlLMG. When comparing the uorescence with the aqueous solution, AlLMG illustrates nearly the same spectrum in n-hexanol extract, except a slight shift of maximum emission wavelength from 595 nm in aqueous phase to 580 nm in n-hexanol solution (Fig. 1). Moreover, no emission signal is observed for n-hexanol at 580 nm, but AlLMG uorescence in n-hexanol can be enhanced by almost 20-fold compared to that in aqueous solutions. This demonstrates one of the advantages compared to the analysis in aqueous solution because the sensitivity can be signicantly improved by the extraction of AlLMG into n-hexanol. The extraction of natural water samples (river water and seawater) by n-hexanol without LMG has no uorescent signal, which indicates that natural uorescent materials have no inuence on the determination of AlLMG in n-hexanol [10]. We measure, therefore, the uorescence of AlLMG after extraction into n-hexanol in this study. 3.1.2. Effect of pH The inuence of sample pH on the uorescence of AlLMG extraction into n-hexanol is investigated. The sample pH is adjusted by diluted hydrochloric

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Fig. 1. Spectra of excitation (ex) and emission (em) of AlLMG in n-hexanol (a), which show blank, 0.3 and 1.0 nM responses. The calibration data, including blank and concentrations near detection limit are also given (b). Experimental condition: 200 ml of Milli-Q water with various Al and 1 mg l1 of LMG, extracted by 10 ml of n-hexanol.

acid and aqua ammonia to cover a wide range from pH = 2 to pH = 9; sample uorescence intensities are recorded at the maximal excitation and emission wavelengths as mentioned above. In Fig. 2, the uorescence of ALLMG in n-hexanol is plotted against the sample pH, the emission data are blank-corrected to minimise the contribution from change in acid, base, and buffer components. The results show the optimal uorescence response at pH = 4.55.5. Further increase or reduction in pH will result in a rapid decrease in uorescent intensity. The optimal pH range obtained is similar to that reported by Hydes and Liss [3] and Howard et al. [13] for aqueous solution measurements, which suggests that the extraction efciency (i.e. uorescence) is largely affected by the pH value of optimal combination of Al and LMG. At pH = 5.0, the uo-

Fig. 2. Effect of aqueous solution pH on the uorescence of AlLMG extraction into n-hexanol. Experimental condition: 100 ml of Milli-Q water with 1.8 M of Al and 2 mg l1 of LMG, extracted by 30 ml of n-hexanol. The gure shows data points and standard deviation (1 ).

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Fig. 3. Effect of amount of LMG on the uorescence of AlLMG in n-hexanol. Experimental condition: 100 ml of Milli-Q, pH = 5.0, Al 0.9 M, Be2+ 150 M, o-phenanthroline 8 M, extracted by n-hexanol (5 ml 4). The gure shows data points and standard deviation (1 ).

Fig. 4. Effect of temperature (25 and 80 C) and reaction time on the uorescence of AlLMG in n-hexanol. Experimental condition: 100 ml of Milli-Q, Al 1.0 M, LMG 2 mg l1 , pH = 5.0, Be2+ 150 M, o-phenanthroline 8 M, extracted by n-hexanol (5ml 4). The gure shows data points and standard deviation (1 ).

rescence is found to reduce approximately by 510% with pH = 1.0 unit, hence the extraction is undertaken at pH = 5.0 0.5 throughout the experiments. The NaAcHAc buffer solution provides an adequate pH = 5.0 0.1 for the analytical procedure. 3.1.3. Amount of LMG It was observed that the uorescence of a system (i.e. 100 ml) containing 2 M of Al reaches a maximum when the amount of LMG is 0.81.2 ml (LMG: 0.02%), that is, with LMG concentrations of 1.52.5 mg l1 [9]. At an Al level of 0.9 M, the maximal uorescence was observed at an LMG level of 0.5 ml; further increase (e.g. 1.0 ml) or decrease (e.g. 0.25 ml) in the amount of LMG leads to a reduction in uorescence by 6.5 and 4.7%, respectively (Fig. 3). Thus, an apparent Al : LMG molar ratio for the reaction is 1 : 3. In a system with high LMG and low Al (i.e. overdose of LMG), the radiation adsorption by excess LMG at AlLMG emission wavelength becomes signicant, which leads to a non-linearity of the calibration graph, while the lack of LMG in the extraction system would reduce the extraction recovery of Al, followed by a decrease in uorescence signals. It is possible to expand the linear range of calibration graph by a slight increase in the amount of LMG, with an expense of a limited reduction in precision. For example, within a precision of 5%, the Al to LMG ratio may vary between 1 : 6 and 2 : 3, that is, by a factor of 45. An LMG concentration of 2.0 mg l1 (i.e. 1 ml of LMG in 100 ml of sample) is

hence adopted in this study, which satises a linear range of calibration graph up to 2 M of Al. 3.1.4. Kinetics and stability of the AlLMG complex The kinetics of extraction chemistry was investigated by measuring uorescence intensity against temperature change at 25 and 80 C, respectively. It was found out that, within the rst 30 min of reaction, the uorescence intensity could be two-fold higher at 80 C than at 25 C; the difference in uorescence intensities then decreases with the duration of reaction. After 2 h, the difference in uorescence between 25 and 80 C reduces to 5% (Fig. 4). It is evident that an increase in temperature facilitates to the removal of ALLMG into n-hexanol; the liquidliquid extraction should be operated after Al is chelated with LMG at a relatively high temperature (e.g. 80 C) to speed up the routine sample analyses. At a given temperature (e.g. 80 C), the uorescence increases slightly faster for Milli-Q water than natural water samples (e.g. seawater). For both fresh water and seawater samples, the uorescence reaches the maximum at 6090 min, and then tends to be stable over 48 h, with a slight difference of only about 1% between distilled water and seawater. Samples treated at 25 C could reach the same uorescence as at 80 C if left over 2 h. The reaction time is set at 90 min, therefore, to provide a fairly high and stable uorescence and to reduce the artefacts due to the differences

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Table 2 Experiment of potential interference elements in the determination of Al by liquid-liquid extractiona Ions Concentrations (nM) River water Seawater Cu2+ Zn2+ Ga3+ Mn2+ Be2+ Fe3+ Ca2+ Mg2+ B3+ (H3 BO3 ) F PO4 3 SiO3 2 SO4 2
a

Level of Recovery of interferant Al (%) (nM) 236 765 28.7 546 150103 900 25.0 106 61.7 106 925 103 78.9 103 18 103 2 106 62.5 106 98.0 96.6 102.7 103.3 98.6 91.5 99.2 99.7 101.1 61.0 99.4 97.8 99.7

23.6 459 1.3 149 5.663.3 716 332 103 128 103 1.7 103 10.5 103 102 103 141 103 91 103

0.52.0 0.16.1 0.3 0.4 0.0040.03 0.180.72 10.3 106 53.1 106 411 103 68.4 103 50100 10 103 28.1 106

Experimental condition: 100 ml of Milli-Q water, Al 0.9 M (for the Fe case, Al was 0.3 M), LMG 2 mg l1 , extraction of 5 ml 4 at pH = 5. Data of interfering ions in natural waters are from [15,16].

in emission intensity between laboratory calibration standards (e.g. Milli-Q) and real water samples (e.g. seawater). 3.2. Interferences A series of 13 major and trace elements in natural waters is tested for the method developed here, including those reported previously as potential interferants in the aqueous AlLMG uorescence measurements [3,1214]. Among the species tested, most of the ions show no interference in the determination of Al by liquidliquid extraction, only Fe3+ (8.5%) and F (39%) could signicantly reduce the uorescence of AlLMG in n-hexanol (Table 2). We believe that the lack of interference for most of the ions exhibited in the system is due to the different chemical condition and liquidliquid extraction in combination as compared to previous studies in the literature. Iron and uorine are known to interfere with the direct uorimetric analysis of Al in aqueous samples, which, until now, is not overcome [3,12,13]. The interference of iron results from the fact that Fe3+ may combine with LMG (FeLMG), which reduces the effective concentration of LMG, leading to a de-

Fig. 5. Elimination of interference from iron on the determination of Al in natural waters. (a) 100 ml of Milli-Q at pH = 5.0, Al 0.3 M, LMG 2 mg l1 , Fe3+ 0.9 M, extracted by n-hexanol (5 ml 4). (b) 100 ml of Milli-Q at pH = 5.0, Al 0.3 M, LMG 2 mg l1 , o-phenanthroline 8 M, extracted by n-hexanol (5 ml 4). Experiments with seawater also show similar results.

crease in the linear range of calibration. FeLMG demonstrates a higher absorption than AlLMG at an excitation wavelength of 500 nm, which dramatically reduces the photon ux of radiation and emission signal at 580 nm [9]. The interference of iron in the determination of Al is more important for fresh water samples than seawater because the concentration of Fe in fresh water can be two to three orders of magnitude higher. Fig. 5 shows the effect of o-phenanthroline on the interference of Fe3+ in the determination of AlLMG in n-hexanol. Clearly, with the presence of o-phenanthroline, the determination of Al in n-hexanol is relieved. For example, with a concentration of 8 M of o-phenanthroline, the determination of Al is free from interference of Fe3+ even at an Fe level up to 1000 nM. Moreover, the blank level of o-phenanthroline solution is low, and the combination between Fe3+ and o-phenanthroline is fast and stable over the time scale of analysis [10].

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mination. The reaction of Be2+ and F is fast and the products are stable in analytical procedure [10]. Moreover, the addition of Be2+ , as well as o-phenanthroline, in samples does not affect the efciency of extraction of AlLMG into n-hexanol. In this study, we did not examine directly, as for the inorganic species, the inuence of various natural organic materials on the determination of Al because there is no commercial compound available that could represent the composition of dissolved organic materials in natural water. The potential effect of organic materials on Al analysis is tested by the intercalibration using natural samples in which organic materials cover a wide range of concentrations, which will be discussed later. 3.3. Matrix effects In order to identify the inuence of changing sample matrices on the determination of Al in natural waters (e.g. fresh water and seawater), a series of calibration graphs was prepared with an Al concentration up to 0.75 M, including Milli-Q water, samples from the Changjiang (Yangtze River), seawaters from East China Sea and South China Sea, and a 1 : 1 volume mixture of Changjiang and East China Sea samples (Fig. 7). When the slope of calibration curves from various matrices (ki ) are compared to that in Milli-Q water (kMilli-Q ), the ki /kMilli-Q ratio varies between 0.93 and 1.02. Given the fact that eld sample collection and ltration may induce an uncertainty of 1020% in marine environment, this result indicates that calibration curves are almost identical for various matrix compositions. The implication includes that the matrix effect on the determination of Al has been minimised, and Al concentration in natural waters can be obtained via the calibration curve from Milli-Q water and uorescence measurement for samples, and the incremental addition procedure is not necessary any more. 3.4. Extraction procedure and calibration The experiments are undertaken to optimise the extraction procedures, including time and frequency of extraction. Table 3 shows that increasing extraction frequency but a small amount of n-hexanol could enhance the recovery of sequential extraction and reduce

Fig. 6. Elimination of interference from uoride on the determination of Al in natural waters. (a) 100 ml of Milli-Q at pH = 5.0, Al 0.9 M, LMG 2 mg l1 , F 79 M, extracted by n-hexanol (5 ml 4). (b): 100 ml of Milli-Q at pH = 5.0, Al 0.9 M, LMG 2 mg l1 , Be2+ 150 M, extracted by n-hexanol (5 ml 4). Experiments with seawater also show similar results.

The interference of F on the determination of Al is due to the fact that this element could strongly combine with Al as AlFx (x 3) (x: 16) in natural waters, and Al may not be necessarily released from AlFx (x 3) and measured by the traditional uorimetric method. The interference of F is more important in marine samples than in fresh water environment because F is ve- to 10-fold higher in seawater than in the river. The inuence of F can be reduced by increasing extraction times and the addition of a cation (e.g. Be2+ ) that could release Al from AlFx (x 3) before extraction. Fig. 6 shows the determination of Al in solutions containing various amount of F . When Be2+ is introduced into the system, the interference of F can be largely reduced. For example, with 150 M of Be2+ , the presence of F does not interfere with the AlLMG uorescence in n-hexanol even at a concentration as high as 80 M. Also, the Be2+ solution has a negligible blank level that does not affect Al deter-

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Fig. 7. Calibration graphs obtained by extraction procedure from various aqueous samples. Note that Al in natural water samples is not subtracted from uorescence record in these calibration curves, and the calibration curves may not necessarily, therefore, pass through 0. Experimental condition: 100 ml of sample at pH = 5.0, LMG 2 mg l1 , Be2+ 150 M, o-phenanthroline 8 M, extracted by n-hexanol (5 ml 4). Four kinds of samples were used in the experiment, that is, Milli-Q water, seawater from East China Sea, a mixture (1 : 1 v/v) of Changjiang (Yangtze River) and East China Sea samples (CJ + ECS), and water sample from Changjiang. Samples from the South China Sea have a calibration curve similar to that of the East China Sea, and hence, are not included in the gure.

further indicate that the Al could be retrieved quantitatively when the extraction time is >1520 s followed by 3060 s of separation between organic and aqueous fractions. In this study, we set the extraction of 90 s with a separation time of 120 s to guarantee quantitative determination and reproducible results. The linear range of calibration curve depends on the concentration of Al in water samples and the pre-concentration factors adopted. When extracted four times with 5 ml of n-hexanol, it is certain that a linear range of calibration curve up to 1 M of Al for an aliquot of 200 ml and up to 2 M of Al for a 100 ml aliquot will be obtained. This concentration covers a fairly wide range of natural water samples, for which Al can be measured versus calibration curve in Milli-Q water through change in the pre-concentration factors, which is easy to practice. 3.5. Recovery and precision The recovery of the present method is examined via Al spikes added to the various natural water samples, including rainwater, river water, seawater, and a mixture (1 : 1 v/v) of river water and seawater samples to represent estuarine waters (Table 4). As shown in the Table 4, all samples analysed here provide evidences of satised recovery, that is, 92.7104%. Moreover, the analysis of eight replicates of riverine and marine samples shows a variation coefcient of 2.7% at 0.74 M of Al, and 4.9% at 40 nM of Al, respectively, in routine analyses. The reproducibility (n = 8) of the present study is 6.3% at an Al content of 5.0 nM, and 6.7% at 1.0 nM of Al, respectively; the linearity at the low end of the calibration range is given in Fig. 1. 3.6. Blank levels and detection limit The main source of blanks in the present liquid liquid extraction method is from the buffer solution. The NaAcHAc buffer solution is puried by the extraction of a trace amount of AlLMG with n-hexanol before use, which can dramatically reduce the blank levels. The detection limit is estimated by the blank level and standard deviation. A series of 10 replicates of Milli-Q water plus reagents yields a concentration of 2.15 0.08 nM (mean ), indicating an estimate of

the nal volume of organic phase, hence increasing the enrichment factor. For example, compared to the 10 and 20 ml extractions, the four-times extraction with 5 ml of n-hexanol each could provide an extraction efciency of 98.5% (Table 3). The experimental results
Table 3 Effect of volume and sequence on the liquidliquid extraction by n-hexanol for Al analysisa Extraction Fluorescence intensity Organic fraction Aqueous fraction 5 ml 1 5 ml 2 5 ml 3 5 ml 4 5 ml 5 10 ml 1 10 ml 2 20 ml 1
a

Extraction (%)

10.29 9.150 7.750 6.530 5.715 8.765 6.055 5.530

0.171 0.050 0.016 0.006 0.003 0.085 0.022 0.078

60.4 88.5 96.3 98.6 99.3 80.3 94.9 82.7

Experimental condition: Milli-Q water 100 ml, Al 0.9 M, LMG 2 mg l1 , pH = 5.0. The aqueous fraction is measured after extraction.

J. Zhang et al. / Analytica Chimica Acta 405 (2000) 3142 Table 4 Efciency of the extraction of dissolved Al in natural water samplesa Sample Yalujiang East China Sea (ECS) Yellow Sea Character hw sw sw Al level (nM) 77.8 344.7 85.2 Al added (nM) 185.3 370.6 185.3 370.6 185.3 370.6 556.0 741.3 185.3 556.0 185.3 370.6 741.3 74.1 185.3 74.1 185.3 185.3 741.3 185.3 370.6 185.3 370.6 741.3 Al measured (nM) 263.2 444.8 537.4 693.1 266.9 441.1 630.1 789.5 689.4 1030 459.6 633.8 978.5 581.9 700.5 155.7 263.2 240.9 756.1 311.3 493.0 378.1 526.3 897.0 Recovery (%) 100.1 99.0 104.0 94.0 98.1 96.0 98.0 95.0 94.0 92.7 94.0 94.0 93.5 95.0 102.0 95.5 95.9 101.6 95.3 95.5 96.4 104.1 95.9 97.6

39

Changjiang (CJ) CJ + ECS (1 : 1 v/v)

hw hw + sw

515.2 285.4

Rainwater East China Sea South China Sea Jiaojiang Estuary Jiaojiang

rw sw sw ew hw

511.5 89.0 51.9 140.8 177.9

Sample character: ew estuarine water, hw river water, rw rain water, and sw seawater.

a detection limit of 0.25 nM (3 ). This level is much lower than the original AlLMG method (37 2 nM) and its recent applications [3,7]. The detection limit reached is also lower than most of the other current methods in the literature, like uorimetric determination (3.7 nM) [14], GC detection (0.6 nM) [17], FIA-spectrouorimetric determination (11 nM) [18], FIA-uorescent detection (3.7 nM) [19], and HPLC determination (1.9 nM) [20]. Rather, the detection limit of this study is similar to recent developments of the LMG method, such as 0.15 nM [12], and even close to the up-to-date detection limit of 0.09 nM reached by ETAAS determination and solvent extraction in combination [11]. However, compared to other current uorimetric determinations in the literature, the present method shows a unique character of freedom from interference of uoride and iron, and is without matrix effect as well. The improved limit

of detection (LOD) of the present method is a result of the liquidliquid extraction which leads to an enrichment factor of up to 20, measurement of uorescence in n-hexanol which enhances the sensitivity, and reduces blanks in combination. We expect that the blank level and the detection limit will be further improved if the method is combined with automatic techniques, like FIA and/or CA.

3.7. Inter-laboratory calibration and analysis of international standard To test if the present method is robust, a series of 1520 samples representing rainwater, riverine, estuarine and marine waters is selected for an inter-calibration practice (Table 5). These samples cover a wide range of matrix composition, concen-

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J. Zhang et al. / Analytica Chimica Acta 405 (2000) 3142

Table 5 Determination of Al in natural waters with liquidliquid extraction (I), standard addition technique (II), and ETAAS (III)a Sample Chlorinity (%) 18.04 18.20 0 0 0.06 0.23 7.50 0.01 1.64 11.17 0.05 8.87 13.62 0.03 5.70 13.95 0.005 0.001 Fe ( M) F ( M) DOC ( M) Concentration of Al ( M) I <0.09 <0.09 1.49 0.75 2.24 1.49 0.09 7.48 5.94 0.75 5.73 3.44 0.32 0.75 3.72 0.23 2.24 1.49 30.7 37.8 13.5 5.05 53.9 53.9 58.3 7.21 12.0 31.0 12.5 33.6 37.8 24.1 34.9 21.7 23.5 5.26 80 170 0.104 0.093 0.715 0.463 1.96 1.78 1.17 1.34 0.308 0.259 1.52 1.87 1.60 0.415 0.152 0.170 1.72 0.208 II 0.111 0.089 0.704 0.441 2.06 1.85 1.15 1.30 0.326 0.252 1.58 1.80 1.56 0.408 0.145 0.163 1.77 0.196 III 0.115 0.100 0.778 0.500 2.13 1.90 1.24 1.44 0.334 0.278 1.65 1.95 1.69 0.448 0.167 0.189 1.82 0.226 Differences (%) I and II 6.7 4.2 1.6 5.0 4.9 3.6 2.3 3.4 5.7 6.1 3.8 3.9 2.8 1.8 5.1 5.5 2.7 5.7 I and III 9.7 7.4 8.8 7.4 8.0 6.4 5.7 7.0 7.8 6.7 7.9 4.2 5.3 7.4 8.9 9.8 5.5 8.2

Yellow Sea East China Sea Rainwater 01 Rainwater 02 Shuangtaizihe 02 Shuangtaizihe 29 Shuangtaizihe 25 Yalujiang 05 Yalujiang 16 Yalujiang 21 Luanhe 02 Luanhe 06 Luanhe 07 Jiaojiang SY03 Jiaojiang P14 Jiaojiang P10 Huanghe Changjiang
a

200 240 175

250 125

The samples include fresh water (rain and river), seawater (chlorinity >18%), and estuarine water (chlorinity: 018%).

tration of potential inference elements (e.g. iron and uoride), dissolved organic carbon (DOC), and are analysed to determine concentrations of Al by the present method (I), the traditional LMG method with standard addition procedure (II), and ETAAS (model: PE4100ZL) determination (III). The differences between this method (I) and method II, and between methods I and III are 510% for all samples tested here, with a concentration range up to two orders of magnitudes for iron and uoride in these waters and salinity from 0 to 34.5 (Table 5). Moreover, the DOC of these samples can be up to 250 M as determined in the laboratory (Table 5). Data in Table 5 further conrm that the extraction technique developed here does not suffer from the matrix effect, interference from Fe3+ , F , and DOC in natural waters. This makes the method most suitable for the analysis of water samples from estuary, where the matrix composition and interference change from sample to sample, and the standard addition technique had to be applied in previous publications [7,8]. It should be kept in mind, however, that data of methods I and II are very close to each other, which are somewhat lower than determinations by ETAAS (i.e. method III). The statistical analyses (t-test) indi-

cate that the data obtained by liquidliquid extraction (I) and standard addition (II) are identical (p = 0.05), while ETAAS determination (III) is statistically higher than both methods I and II (p = 0.05) [21]. Apparently, such a positive bias by ETAAS indicates a systematic difference. While in ETAAS, the atomisation at 25003000 C may decompose organic and colloidal materials and hence determine total dissolved Al, in the AlLMG uorimetric determination at ambient temperature, the labile or non-colloidal/non-organic combined Al tends to be analysed. A rather limited difference between data from methods I, II, and III in Table 5 suggests, however, that such a difference is in part due to analytical uncertainties (e.g. 5%). The contribution of organic and colloidal/organic materials to total dissolved Al, if there is any, is limited to 510% for the samples in Table 5, probably due to the poor afnity of Al with organic material in natural waters. The certied value for Al is still not available in commercially international seawater standards, thus a US standard sample SRM 1643C is used in this study and the concentration of Al is determined with the proposed extraction method and compared with the value obtained by ETAAS at the Oceanography Laboratories, The University of Liverpool (PerkinElmer

J. Zhang et al. / Analytica Chimica Acta 405 (2000) 3142 Table 6 Analysis of international reference materials and the inter-calibration with two rainwater samples among three laboratoriesa Sample This method Liverpool a SRM 1643C Rain LRW 43 Rain LRW 45
a

41

Qingdao b 113.2 3.0 25.0 1.2 16.2 0.7

Average (a + b)/2 113.2 3.0 24.6 1.2 16.2 0.7

Differences (%)

109.7 2.5 23.4 0.6 15.1 0.4

113.2 3.0 24.2 0.7 16.3 0.4

3.1 4.9 6.4

Concentration of Al:

g l1 , rain water samples were collected from the campus of The University of Liverpool.

model: 1100B), and the Institute of Oceanography, Academic Sinica (PerkinElmer model: 4100ZL) (Table 6). The certied value of Al for SRM 1643C standard is 114.6 5.1 g l1 , the proposed uorometric method gives a value of 109.7 g l1 , and ETAAS provides a value of 113.2 g l1 , respectively. Two rainwater samples analysed both at Liverpool and Qingdao show that data of Al from three laboratories compare well (Table 6). Again, the statistical evaluation using t-test (p = 0.05) for the data in Table 6 conrms that the analysis of SRM 1643C standard in the three laboratories is in agreement with the certied value, and the data from three laboratories for calibration samples (i.e. rain water) do not statistically differ from each other (Table 6).

1643C standard and inter-calibration for a variety of natural water samples shows the robust character and reliability of the present method. Finally, the successful inter-laboratory calibration practice indicates that data of Al from the present method are well consistent with and readily comparable to those from other methods and/or laboratories, and data from the literature.

Acknowledgements This study was funded by the Natural Science Foundation of China (NSFC No. 49576297 and 49525609). The authors thank Dr. J.F. Li and Dr. Z.N. Zhang for uorimetric measurements, and Dr. Q. Wang and Dr. P. Corcoran for ETAAS determinations. Dr. P. Worsfold and two anonymous reviewers are acknowledged for their critical comments that greatly improved the original manuscript. References
[1] Y. Nishikawa, K. Hiraki, K. Morishige, T. Shigematsu, Japan Analyst 16 (1967) 692 (in Japanese). [2] Y. Nishikawa, K. Hiraki, K. Morishige, A. Tsuchiyama, T. Shigematsu, Japan Analyst 17 (1968) 1092 (in Japanese). [3] D.J. Hydes, P.S. Liss, Analyst 101 (1976) 922. [4] D.J. Hydes, Geochim. Cosmochim. Acta 47 (1983) 967. [5] A.W. Morris, R.J.M. Howland, A.J. Bale, Geochim. Cosmochim. Acta 50 (1986) 189. [6] D.J. Hydes, P.S. Liss, Cont. Shelf Res. 13 (1993) 1083. [7] S. Upadhay, R.S. Gupta, Mar. Chem. 51 (1995) 261. [8] L. Chou, R. Wollast, Water Poll. Res. Reports 20 (1990) 361. [9] H. Xu, M.Sc. Dissertation, The Ocean University of Qingdao, Qingdao, 1995, p. 85 (in Chinese). [10] J.L. Ren, M.Sc. Dissertation, The Ocean University of Qingdao, Qingdao, 1998, p. 91 (in Chinese). [11] K.J. Orians, K.W. Bruland, Earth Planet Sci. Lett. 78 (1986) 397.

4. Conclusions LMG is a commercially available reagent that is able to form a highly uorescent complex with Al; this character allows the uorimetric determination of Al in natural waters. However, the traditional uorimetric method suffers from the matrix effects and interference of major and trace components, notably iron and uoride. Coupled with liquidliquid extraction into n-hexanol, the present study provides a better technique to determine trace amount of dissolved Al in natural waters, with a detection limit of 0.25 nM. The present method is simple and it can be applied to the routine analyses in an ordinary/modest laboratory. Reasons for the improved LOD include liquidliquid extraction into n-hexanol that signicantly enhances the sensitivity of AlLMG and reduces the matrix effect. The application of o-phenanthroline and Be2+ solutions eliminates the interference of Fe3+ and F , further increasing the selectivity. The analysis of SRM

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J. Zhang et al. / Analytica Chimica Acta 405 (2000) 3142 [17] C.I. Measures, J.M. Edmond, Anal. Chem. 61 (1989) 544. [18] P. Fernandez, C.P. Conde, A. Gutierrez, C. Camara, Talanta 38 (1991) 1387. [19] S.H. Sutheimer, S.E. Cabaniss, Anal. Chim. Acta 303 (1995) 211. [20] C.Y. Zhou, J. Wu, H. Chi, M.K. Wong, L.L. Koh, Y.C. Wee, Talanta 42 (1995) 415. [21] S.J. Haswell, in: S.J. Haswell (Ed.), Practical Guide to Chemometrics, Marcel Dekker, New York, 1992, p. 5.

[12] J.A. Resing, C.I. Measures, Anal. Chem. 66 (1994) 4105. [13] A.G. Howard, A.J. Coxhead, I.A. Potter, A.P. Watt, Analyst 111 (1986) 1379. [14] J.M. Escriche, F.H. Hernandez, Analyst 110 (1985) 287. [15] J.M. Martin, V. Gordeev, in: Estuarine Processes: An Application to the Tagus Estuary, UNESCO/IOC/CAN, Lisbon, 1986, p. 203. [16] Department of Marine Chemistry (OUQ), Chemical Oceanography, Press of Ocean University of Qingdao, Qingdao, 1995, p. 27 (in Chinese).