Sie sind auf Seite 1von 16

This article was downloaded by: [Florida State University] On: 26 March 2013, At: 18:01 Publisher: Taylor

& Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Analytical Letters
Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/lanl20

Determination of Total Arsenic in Wastewater and Sewage Sludge Samples by Using Hydride-Generation Atomic Fluorescence Spectrometry Under the Optimized Analytical Conditions
Guobing Luo
a a

Water Quality Monitoring Station, Wuxi Drainage Company, Wuxi, China Accepted author version posted online: 17 May 2012.Version of record first published: 20 Nov 2012.

To cite this article: Guobing Luo (2012): Determination of Total Arsenic in Wastewater and Sewage Sludge Samples by Using Hydride-Generation Atomic Fluorescence Spectrometry Under the Optimized Analytical Conditions, Analytical Letters, 45:17, 2493-2507 To link to this article: http://dx.doi.org/10.1080/00032719.2012.694131

PLEASE SCROLL DOWN FOR ARTICLE Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. The publisher does not give any warranty express or implied or make any representation that the contents will be complete or accurate or up to date. The accuracy of any instructions, formulae, and drug doses should be independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims, proceedings, demand, or costs or damages whatsoever or howsoever caused arising directly or indirectly in connection with or arising out of the use of this material.

Analytical Letters, 45: 24932507, 2012 Copyright # Taylor & Francis Group, LLC ISSN: 0003-2719 print=1532-236X online DOI: 10.1080/00032719.2012.694131

Environmental Analysis DETERMINATION OF TOTAL ARSENIC IN WASTEWATER AND SEWAGE SLUDGE SAMPLES BY USING HYDRIDE-GENERATION ATOMIC FLUORESCENCE SPECTROMETRY UNDER THE OPTIMIZED ANALYTICAL CONDITIONS
Downloaded by [Florida State University] at 18:01 26 March 2013

Guobing Luo
Water Quality Monitoring Station, Wuxi Drainage Company, Wuxi, China
In this work, an improved hydride-generation atomic uorescence spectrometry (HG-AFS) method for the determination of total arsenic (As) in wastewater and sewage sludge samples was applied. The samples were digested completely with mixtures of HNO3 and HClO4. Analytical conditions were studied and optimized through uniform experimental design U10 108 combined with a single factor test. A mathematical model was established, and a quadratic polynomial stepwise regression analysis by using the DPS software was employed to obtain the factors that impact the uorescence intensity. This technique is then combined with a single factor test. The optimized experimental conditions were obtained as follows: PMT voltage was 305 V, lamp current was 70 mA, KBH4 concentration was 2.0% (m/v), carrier liquid (HCl) concentration was 5% (v/v), carrier gas (Ar) ow rate was 300 mL min1, and reaction acidity was 10% (v/v) HCl. The pre-reduction of all forms of As to As(III) was performed by using a mixed solution of 1% thiourea and 1% ascorbic acid. The content of total As was determined under the optimized experimental conditions. The detection limits for total As in wastewater and sewage sludge were 0.09 lg L1 and 0.01 mg kg1, respectively. The linear ranges were 0.24100 lg L1, and the recovery was 91.0102.0%. The relative standard deviation (RSD, n 5) for eleven replicate measurements of the certied reference materials containing 60.6 4.2 lg L1 As (certied sample of water) and 10.7 0.8 mg kg1 As (certied sample of soil) were 3.1% and 1.6%, respectively. The proposed method was validated by the analysis of certied reference materials and was successfully applied to the determination of total As in real samples of wastewater and sewage sludge with satisfactory results. Keywords: Hydride-generation atomic uorescence spectrometry; Sewage sludge; Single factor test; Total As; Uniform experimental design; Wastewater

Received 29 March 2012; accepted 8 May 2012. I would like to thank Prof. Xianzhong Cheng, Xiuping Yan, and Jianhua Wang for their constructive suggestions. Address correspondence to Guobing Luo, Water Quality Monitoring Station, Wuxi Drainage Company, Wuxi 214011, Peoples Republic of China. E-mail: gbluo324@163.com 2493

2494

G. LUO

INTRODUCTION Arsenic is widely distributed in the environment (Reyes et al. 2008). Arsenic and most of its compounds are highly toxic. The inorganic forms are far more toxic than their organic counterparts (Reyes et al. 2007). The toxicity of As (III) is 1020 times higher than that of As (V) (Bissen and Frimmel 2003; Wu et al. 2011). Arsenic has potential risks to human health. Even low intake levels of As can cause serious effects to the human body (Guo et al. 2011; Shah et al. 2009; Islam et al. 2004). The International Agency for Cancer Research has considered As as a carcinogen (Wu et al. 2011; El-Hadri, Morales-Rubio, and de la Guardia 2007; DAmato et al. 2011). The release of its compounds in wastewater is associated with a variety of industrial processes, such as the production of metallurgical, mining, pesticides, chemicals, and glass. Wastewater contained As is drained into sewage treatment plants through the wastewater pipe network. Parts of As in wastewater is precipitated gradually into the sewage sludge. Arsenic in sewage sludge is very difcult to degrade and get rid from the processing of incineration, landll, brick, and compost. Its content directly affects the pollution-free disposal of sewage sludge. Total As is one of the total amounts of emissions control targets of China, and is listed as the rst class of pollutants. Because of its toxicity and pollution, it is important to determine total As in wastewater and sewage sludge samples. Hydride-generation atomic absorption spectrometry (HG-AAS) is the international standard to determine As in both water, following International Organization for Standardization (ISO) method 11969 (ISO 1996), and soil, following ISO method 20280 (ISO 2007). The Chinese standard still adopts expired ISO methodsilver diethyldithiocarbamate (Ag-DDC) spectrometry (MEP 1987) to determine As in water. However, the Ag-DDC method provides unstable test results and requires a large amount of CHCl3 with high toxicity. Furthermore, it also has some disadvantages including demand of many reagents, complexity, and low efciency (one element per test). Now the Chinese standard has already adopted hydridegeneration atomic uorescence spectrometry (HG-AFS) (AQSIQ 2008) to determine mez-Ariza As in soil. HG-AFS has been described to be superior to HG-AAS (Go nchez-Rodas et al 2010) owing to its good sensitivity et al. 1999; Heilier et al. 2005; Sa mez-Ariza et al. and wide linear calibration range (from mg L1 to mg L1) (Go 1998; Jiang et al. 2008; Moscoso-Perez et al. 2004; Xing et al. 2009), with further mez-Ariza advantages (rapid, simplicity, excellent choice, and running costs [Go et al. 2000a; Lindberg et al. 2007; Bings, Bogaerts, and Brokekaert 2010; Wang et al. 2004; Tang, Xu, and Wang 2005]) for As speciation in routine analysis. HG-AFS is well suited for the determination of hydride-forming elements (Tang, Xu, and Wang 2005) and has been successfully applied to the determination of As in seawater, foods, soil samples, tea leaves, herbarium mount paper, wastewater, nchez-Rodas human urine, and so forth (Wu et al. 2011; DAmato et al. 2011; Sa et al 2010; Correia et al. 2010; Wang and Zhang 2011; Zhang et al. 2011; Lummas et al. 2011; Luo et al. 2005; Wietecha-Posluszny, Dobrowolska, and Koscielniak 2006). For many of the wastewater samples, the concentration of As might be very low. In such circumstances, the insufcient detection sensitivity and the matrix effects affect the accuracy of the determination of total As. In addition, the

Downloaded by [Florida State University] at 18:01 26 March 2013

DETERMINE TOTAL AS BY AFS WITH TWO CONDITION TESTS

2495

compositions of sewage sludge samples are more complicated than that of above-mentioned samples, such as soil and wastewater due to the high content of organic matters. Thus, the rst and crucial stage in total As analysis is sample treatment, whereby the various forms of the analyte present are extracted nchez-Rodas et al. 2010; Loska and Wiechula 2006; Go mez-Ariza et al. 2000b). (Sa Up to now, there have been no relevant reports on the determinations of total As in wastewater and sewage sludge samples by using one method of complete digestion. Aqua regia digestion is recommended, following ISO method 11466 (ISO 1995) and Deutsches Institut fu r Normung and European Committee for Standardization (DIN EN) method 16174 (DIN EN 2011) and is very widely employed. Incomplete digestion may be obtained because of insufcient oxidation (Husted et al. 2011). In this work, mixtures of HNO3 and HClO4 were adopted to digest the wastewater and sewage sludge samples on an electric hot plate in a fume hood owing to their strong oxidizing capability, complete digestion, and low cost. The experiment parameters such as photomultiplier (abbreviated PMT) voltage, lamp current, and potassium borohydrid (abbreviated KBH4) concentration impact greatly on the uorescence intensities by using the HG-AFS method to determine As. In order to obtain the best experiment parameter value that affects each factor of the uorescence intensity, an appropriate test design was essential to be considered. According to most previously published papers, single factor tests were generally used to obtain the optimized experimental condition of each factor. However, a particular interaction among various factors exists. Therefore, it is difcult to obtain best experiment parameter values such as PMT voltage, carrier liquid concentration, and carrier gas ow rate by using only single factor tests. Orthogonal design and uniform design are widely used as multi-factor test designs of experimental methods (Fang 1994; Tang and Feng 2007; Liu et al. 2009). The former is characterized by uniformity and decentralization, orderliness and comparable, but it is limited in tests with lower levels (less than 5) (Fang 1994). Uniform design, which is an experimental method combined multivariate statistical theory with number theory by Chinese mathematical statistician Kaitai Fang and mathematician Yuan Wang, was developed on the basis of orthogonal design (Wang and Fang, 1981). Uniform design only seeks design points that are uniformly scattered on the domain. The practical success of uniform design is due to its economical and exible experimental runs to study multi-factors with multi-levels simultaneously (Liu et al. 2009; Ji et al. 2006; Liu and Tang 2010; Liang, Fang, and Xu 2001). In this work, uniform experimental design combined with a traditional single factor test was adopted to optimize the experimental parameters. In the presented work, a method for the determination of total As in wastewater and sewage sludge samples by HG-AFS was established. The proposed method is based on the use of mixtures of HNO3 and HClO4 for sample preparation by an electric hot plate treatment, with the aim of complete digestion. The analytical parameters for the uorescence intensities of total As were investigated by uniform experimental design combined with a traditional single factor test. The optimization of experimental parameters and its analytical performances, as well as its application to the determination of total As in wastewater and sewage sludge samples, were presented in this work.

Downloaded by [Florida State University] at 18:01 26 March 2013

2496

G. LUO

EXPERIMENTAL Instrumentation A model AFS-2202 double-channel, non-dispersive atomic uorescence spectrometer (Beijing Haiguang Instrument Co., Beijing, China) was employed for the determination of As. High-intensity As hollow cathode lamp (General Research Institute for Nonferrous Metals, Beijing, China) was used as the radiation source at 193.7 nm. A single computer was used to control the atomic uorescence spectrometer in order to synchronize the sample processing and the AFS determination. Details of the operating parameters employed in the present investigation for the AFS instrument are summarized in Table 1.

Downloaded by [Florida State University] at 18:01 26 March 2013

Reagents and Samples All chemicals used in this work, were of analytical grade and were all purchased from Sinopharm Chemical Reagent Co., (Shanghai, China). Deionized water which was used for the preparation of all blank, standards, and sample solutions was obtained from a Milli-Q water purication system (Millipore, France). Compressed argon gas of 99.999% purity was used as the carrier and shield gas. The 100 mg L1 standard stock solutions of As was purchased from IERM (Beijing, China). Working standard solutions obtained by stepwise dilution of the stock solutions with deionized water were always freshly prepared. A 1.5% (m=v) KBH4 solution used as the reductant was prepared by dissolving KBH4 in 0.5% (m=v) KOH solution, and this solution was daily prepared and protected from light. A mixed solution of 1% thiourea-1% ascorbic acid (m=v) was used as the prereducing agent. This solution was also daily prepared. The chemicals used for digestions were HNO3 (high purity) and HClO4 (high purity). A 5% (v=v) HCl was used as the carrier liquid. The certied reference materials of GSBZ 50004-88 (certied sample of water) and GSBZ 50011-88 (certied sample of soil) were purchased from IERM (Beijing, China) for evaluating the accuracy of the proposed method. Software of experimental design, statistical analysis, and data mining (abbreviated Software of DPS) (http://www.dpsw.cn/index.htm, Hangzhou, China).

Table 1. Instrument operating parameters Atomizer height Delay time Record mode Shielding gas ow rate 8 mm 1s Peak area 700 mL min1 Determination mode Record time Inject volume Pump rate (rpm) 0 100 0 120 Time (s) 6 10 6 18 Std. curve 10 s 1.5 mL Action No action No action No action Acquire data

The program of intermittent ow system Step Step Step Step 1 2 3 4

DETERMINE TOTAL AS BY AFS WITH TWO CONDITION TESTS

2497

Procedure for Calibration A series of As standard working solutions with the concentration ranging from 0 to 40.0 mg L1 were used for calibration. The working solution was mixed with HCl to a nal concentration of 10% (v=v), and thiourea-ascorbic acid 1% (m=v). After this pre-reduction step, the measuring solutions were submitted to instrumental analysis. They were continuously merged with the reductant by means of the peristaltic pumps. The generated arsine was separated in the gas-liquid separator and carried to the atomizer by an argon ow (Correia et al. 2010). The calibration graphs were prepared by plotting the uorescence intensity (If) against the concentration (C) of total As. Sample Pre-Treatment Wastewater samples were collected at the inlet and outlet of two sewage treatment plants (Wuxi, China). Sewage sludge samples dewatered were also taken from the two plants. A sample of 50 mL wastewater (previously made up to 0.2% (v=v) HCl just after sampling) was accurately pipetted into a 100-mL beaker. Air-dried sewage sludge sample (prepared in accordance with ISO method 11464) (ISO 1995) was grinded and meshed (100 mesh). A representative sample of 20 g was removed. A 0.5000 g sewage sludge sample was accurately weighed into a 100-mL beaker while 5 mL high purity HNO3 and 2 mL high purity HClO4 were added to the wastewater and sewage sludge samples previously mentioned. They were then mixed and heated on an electric hot plate until they gave off a large quantity of white smoke, HNO3. The solutions were cooled to room temperature, and 5 mL 50% (v=v) HCl was added. The samples were heated again on the electric hot plate until they were almost dry. After cooling, the solutions in the breakers were transferred into 50-mL colorimetric tube with a small amount of deionized water to 50 mL. Diluting the digestion solution properly, then added HCl and thiourea-ascorbic acid following the calibration curve program. The nal solution volume was kept at 50 mL. Blanks and calibration solutions were prepared in a similar way in order to achieve the same nal concentrations. After 30 min, the solution was used directly for the determination of total As. Test Scheme Design The experimental parameters for HG-AFS operations had been carefully scrutinized in terms of sensitivity by using As standard solutions of 25.0 mg L1, and the uorescence intensity was employed for quantication. Uniform Experimental Design Many factors inuence the values of the uorescence intensities, mainly PMT voltage (X1), lamp current (X2), KBH4 concentration (X3), carrier liquid concentration (X4), carrier gas ow rate (X5), reaction acidity (X6), and so forth. In this work, these 6 factors were optimized based on uniform experimental design, with uniform design tabulation of U10 108 and corresponding use tabulation (Fang 1994). According to the test schedule, the aforementioned factors were selected.

Downloaded by [Florida State University] at 18:01 26 March 2013

2498

G. LUO
Table 2. Table and results of uniform design U10 108 experiment

No. 1 2 3 4 5 6 7 8 9 10

X1=V 275 280 285 290 295 300 305 310 315 320

X2=mA 45 55 65 75 85 40 50 60 70 80

X3=m=v 1.5 3.0 4.5 0.5 2.0 3.5 5.0 1.0 2.5 4.0

X4=v=v 9 20 7 17 5 15 3 13 1 10

X5=mL min1 600 400 750 550 350 700 500 300 650 450

X6=v=v 20 16 14 12 10 8 6 4 2 1

the uorescence intensity(If) 80.22 150.55 520.72 84.66 2173.22 158.42 346.86 614.51 1964.87 3232.76

Downloaded by [Florida State University] at 18:01 26 March 2013

Note: X1, PMT voltage; X2, lamp current; X3, KBH4 concentration; X4, carrier liquid concentration; X5, carrier gas ow rate; X6, acidity of the reaction medium.

Ten levels were chosen from each factor. The test scheme and test the uorescence intensity are listed in Table 2.

Single Factor Test Within the six factors selected by uniform experimental design, the value of any one factor was changed while keeping the other ve factors xed. The single factor text tested the uorescence intensity of the changed factors in As standard solution.

RESULTS AND DISCUSSION Choice of the Digestion Method The HG-AFS system consisted mainly of two parts, the hydride generator and the AFS detector. Before hydride generation, digestion step was carried out to convert all forms of As to As (III) (Yong 2000). One or more strong oxidizing agent (s) such as aqua regia, HNO3, HClO4, and H2O2 was (were) suggested to digest the wastewater and sewage sludge samples. H2SO4 was rarely used in atomic uorescence analysis for high blank uorescence intensity during the determination and trace As contained during production. However, high content of organic matter in sewage sludge samples results in the oxidation power of aqua regia and H2O2 which were not sufcient to digest the samples completely. HNO3 and HClO4 were available with their strong oxidizing capability with most elements of interest (Husted et al. 2011). This means that mixtures of HNO3 and HClO4 are very effective for digestion of wastewater and sewage sludge samples. On the other hand, the safety should be taken into account by using HClO4 to digest, and HClO4 is only used in open digestion systems such as electric hot plate. Considering the matrix complexity of the sewage sludge samples due to their high content of organic matter, mixtures of HNO3 and HClO4 might be considered as a suitable option, and the electric hot plate digestion was employed in this way.

DETERMINE TOTAL AS BY AFS WITH TWO CONDITION TESTS Table 3. Analytical tabulation of variance Sources of variation Regression Residual Total sum R 0.989 Sum of squares 10919023.210 246860.601 11165883.810 R2 0.978 Degree of freedom f1 5 f2 4 9 Mean square 2183804.64 61715.15 F value 35.39

2499

p value 0.0021

Optimization of Experimental Parameters Regression analysis on the data of uniform experimental design. The uorescence intensity of the inspection object was processed through the DPS software (Tang and Feng 2007), using quadratic polynomial stepwise regression analysis. The gotten binary regression equation is: Y 395305:12 3122:48 1 2462:02 2 6:05 1 X1 8:43 1 X2 18:45 3 X6 From the equations ANOVA table (Table 3), this model proved to be suitable. The predicted and measured values had a high degree of correlation (R 0.989). Checking the critical value table of F, we obtained F0.05 (5, 4) 6.26, F 32.4951; additionally, p < 0.01, which showed that the regression equations were signicant. The regression coefcients of the equations signicance test showed that within the six factors, the other four factors had signicant inuence on the uorescence intensity, excluding carrier liquid concentration and carrier gas ow rate. Optimization of the Six Factors The increase of PMT voltage might improve the sensitivity of detection, but if PMT voltage was too large, it might bend work curve and decreased the linearity locally. Figure 1 showed the impact of PMT voltage on the uorescence intensity. The graph made by the DPS software showed that the uorescence intensity was gradually increased with the increase of PMT voltage, reaching the highest value

Downloaded by [Florida State University] at 18:01 26 March 2013

Figure 1. Effect of PMT voltage on the atomic uorescence intensities of As. (Figure available in color online.)

2500

G. LUO

Downloaded by [Florida State University] at 18:01 26 March 2013

in 300 V, and then the uorescence intensity decreased gradually. The rated voltage (300 V) is recommended by the lamp manufacture. And, it was basically veried by the uniform design test. However, the results of the single factor test showed that with the increase of the PMT voltage, the uorescence intensity increased linearly in the range of 270 to 320 V. Considering the signal-to-noise ratio, a PMT voltage of 305 V was selected. The increase of the lamp current might also improve the sensitivity of detection, but when the lamp current was too large, noise and self-absorption might be produced which could reduce the life of the lamps. Figure 2 shows the impact of lamp current on the uorescence intensity. The lamp current had a linear relationship with the uorescence intensity, as plotted by the DPS software. The rated lamp current (80 mA) is recommended by the lamp manufacture. The uorescence intensity increased with the increase of lamp current within the rated lamp current. From another point of view, the results of the single factor test showed that with the increase of lamp current, the uorescence intensity increased gradually in the range of 40 to 80 mA. The maximal value was at 70 mA; thereafter, with the increasing of lamp current, the uorescence intensity gradually trended to stable and grew slightly. Thus, a lamp current of 70 mA was selected according to lamp life. In the HG-AFS system, KBH4 was employed not only as a reductant but also as a hydrogen supply to sustain the argon-hydrogen ame. Figure 3 showed the impact of the KBH4 concentration on the uorescence intensity. The KBH4 concentration had a linear relationship with the uorescence intensity, as plotted by the DPS software. With the increase of the concentration of KBH4 solution, more As(III) could be prereduced under the test. Thus, the increased uorescence intensity was obtained. However, the results of single factor test showed that the uorescence intensity increased with the increasing concentrations of KBH4 up to 2.0% (m=v). Lower concentrations of KBH4 might give incomplete reduction of the analyte and=or provided insufcient hydrogen to maintain the argon-hydrogen ame, leading to low uorescence intensity. Higher concentrations of KBH4 produced some additional drawbacks, such as high background signals, strong foam causing trouble for separation, and diluting atomic concentration because of more hydride (Li et al. 2011). Considering the sensitivity and accuracy, a KBH4 solution of 2.0% (m=v) was selected.

Figure 2. Effect of lamp current on the atomic uorescence intensities of As.

DETERMINE TOTAL AS BY AFS WITH TWO CONDITION TESTS

2501

Downloaded by [Florida State University] at 18:01 26 March 2013

Figure 3. Effect of KBH4 concentration on the atomic uorescence intensities of As.

Figure 4 shows the impact of the carrier liquid concentration on the uorescence intensity. From the given curve made by the DPS software, the uorescence intensity of As remained constant when the carrier liquid concentration was in the range of 0.5 to 20% (v=v), which veried that the conclusion which the carrier liquid concentration had no signicant inuence on the uorescence intensity from the regression coefcients of the equations signicant test. On the other hand, the result of single factor test showed the uorescence intensity increased gradually in the range of 0.5 to 5% (v=v). The maximal value was obtained at 5% (v=v); thereafter, with the increasing of HCl concentration, the uorescence intensity kept stable. Therefore, a HCl solution of 5% (v=v) as the carrier liquid was employed. In the proposed method, the volatile species of As evolved from the reaction of acidic samples with KBH4 were separated from the solution, and the gaseous products in the gas-liquid separator were swept into the atomizer by an argon gas carrier ow rate. Figure 5 shows the impact of the carrier gas ow rate on the uorescence intensity. From the given curve made by the DPS software, the carrier gas ow rate in the range of 300 to 750 mL min1 had no signicant effects on the uorescence intensity; which maintained good agreement with the regression coefcients of the

Figure 4. Effect of carrier liquid concentration on the atomic uorescence intensities of As.

2502

G. LUO

Downloaded by [Florida State University] at 18:01 26 March 2013

Figure 5. Effect of carrier gas ow rate on the atomic uorescence intensities of As. (Figure available in color online.)

equations signicance test. The result of the single factor test showed the uorescence intensity increased gradually with the increase of the carrier gas ow rate. The higher carrier ow rate of argon gas that increased in the hydride generation efciency was not obvious as the higher carrier ow rate shortened the mixing time of KBH4 and HCl. Based on a compromise between optimum transport efciency and dilution, 300 mL min1 as the carrier gas ow rate was selected. Hydride reaction greatly depended upon the acidity of the reaction (Li et al. 2011). Figure 6 shows the impact of the reaction acidity on the uorescence intensity. The reaction acidity had a linear relationship with the uorescence intensity, as plotted by the DPS software. The uorescence intensity of As gradually increased with the concentration of HCl because more arsine reacted within the acidity range of the test. However, the result of the single factor test showed the uorescence intensity increased quickly when the reaction acidity was from 0.5 to 10% (v=v); higher concentration of the reaction acidity could maintain stablity and slightly decrease the uorescence intensity because of a mass of hydrogen diluting As hydride. Accordingly, an HCl solution of 10% (v=v) as reaction acidity was used.

Figure 6. Effect of reaction acidity on the atomic uorescence intensities of As.

DETERMINE TOTAL AS BY AFS WITH TWO CONDITION TESTS

2503

Pre-Reduction Condition It is well recognized that As(III) has higher efciency of hydride generation than As(V) (Zhang et al. 2011); therefore, the importance of selecting suitable pre-reduction procedures to covert As(V) to As(III) should be considered. To reducing As(V) to As(III), a mixed solution of thiourea-ascorbic acid is commonly used, not only as a prereducing agent but also as a masking reagent, to eliminate the interferences from the transition metal (Li et al. 2008). The thiourea-ascorbic acid concentration was investigated over a range from 0 to 2% (m=v) with prereducing time maintained at 30 min. The results indicated that when the concentration of thiourea-ascorbic acid was 1% (m=v), the uorescence intensity became highest. Thus, a mixed solution of 1% thiourea-1% ascorbic acid (m=v) was sufcient for the achievement of a complete reduction of As.

Downloaded by [Florida State University] at 18:01 26 March 2013

Analytical Performance Under the optimized conditions, the uorescence intensity (If) showed a good linear relationship with As concentration (C) at the concentration range of 0.24100 mg L1. The linear regression equation was If 42.9761C 87.5530, with the correlation coefcient (r) of 0.9998. The detection limits of total As in wastewater and sewage sludge samples were 0.09 mg L1 and 0.01 mg kg1, respectively, calculated as three times the standard deviations of the blank (k 3, N 11).

Interference Study The inuences of 8 coexisting ions on the uorescence intensity of As were investigated with the proposed method in this section. All the tests were carried out under optimum operating conditions and evaluated with an As concentration level of 20 mg L1 and within a 5% error range. A mixed standard solution with the concentration of 20 mg L1 Cu, 20 mg L1 Fe, 2 mg L1 Cd, 10 mg L1 Ca, 5 mg L1 Mg, 10 mg L1 Zn, 10 mg L1 Pb, and 2 mg L1 Pb did not interfere with the determination. The use of chemical reagents did not interfere in the determination of total As in wastewater and sewage sludge samples. Therefore, the method could be employed directly and no masking reagents were necessary.

Analysis of Certied Reference Materials In order to demonstrate the accuracy of the method, the certied reference materials (GSBZ 50004-88 certied sample of water and GSBZ 50011-88 certied sample of soil) were analyzed. The results for the determination of As in these certied reference materials are listed in Table 4 and a good agreement between found and certied values was obtained. The relative standard deviations of GSBZ 50004-88 certied sample of water sample and GSBZ 50011-88 certied sample of soil sample were 3.1 and 1.6%, respectively. Therefore, the proposed method was accurate and reliable.

2504

G. LUO

Table 4. Analytical results for total As in National certied reference material of PR China (n 5) Samples 200431 (GSBZ 50004-88) ESS-1 (GSBZ 50011-88)
a

Certied (mg L1) (60.6 4.2) (10.7 0.8)a

Found (mg L1) (61.2 2.7) (10.6 0.2)a

RSD (%) 3.1 1.6

(mg kg1).

Table 5. Results of determination of total As in wastewater and sewage sludge samples Samples 1# 1# 2# 2# 3# 4#
a

Found (m g L1) 5.04 1.09 22.60 0.00 15.20a 21.90a

Added (m g L1) 5.00 5.00 25.00 5.00 20.00a 20.00a

Total (m g L1) 9.89 5.73 48.10 4.76 33.40a 40.80a

Recovery (%) 97.0 92.8 102.0 95.2 91.0 94.5

Downloaded by [Florida State University] at 18:01 26 March 2013

(inuent) (efuent) (inuent) (efuent) (Sludge) (Sludge) (mg kg1).

Real Analytical Application The present method was applied to wastewater (i.e., inuent, efuent) and sewage sludge samples collected at two sewage treatment plants (Wuxi, China). The analytical results along with the recoveries of the spiked samples are listed in Table 5. The recoveries for spiked wastewater and sewage sludge samples were between 91.0 and 102.0%. A good agreement was obtained between the added and measured values. These results conrmed the validity of the proposed method. CONCLUSION In this manuscript, a HNO3-HClO4 mixed acid system on an electric hot plate for the complete digestion of wastewater and sewage sludge samples was employed; the optimized instrument parameters were obtained by uniform experimental design combined with a traditional single factor test. The results show that this work presents a rapid and simple analytical method for the reliable determination of total As. The procedure has been demonstrated by recovery studies and by the analysis of real samples. The good features of the proposed method showed that it is a convenient and low cost method. This approach provides a viable alternative to the conventional HG-AFS technique for speciation analysis of total As in wastewater and sewage sludge samples for environmental monitoring. REFERENCES
Bings, N. H., A. Bogaerts, and J. A. C. Brokekaert. 2010. Atomic spectroscopy: a review. Anal. Chem. 82: 4656. Bissen, M., and F. H. Frimmel. 2003. Arsenic A review. Part I: Occurrence, toxicity, speciation, mobility. Acta Hydrochim. Hydrobiol 31: 9.

DETERMINE TOTAL AS BY AFS WITH TWO CONDITION TESTS

2505

BS ISO 11464:2006. 2006. Soil quality - Pretreatment of samples for physico-chemical analysis. Geneva, Switzerland: International Organization for Standardization. Correia, C. L. T., R. A. Goncalves, M. S. Azevedo, M. A. Vieira, and R. C. Campos. 2010. Determination of total arsenic in seawater by hydride generation atomic uorescence spectrometry. Microchem. J. 96: 157160. DAmato, M., F. Aureli, S. Ciardullo, A. Raggi, and F. Cubadda. 2011. Arsenic speciation in wheat and wheat products using ultrasound- and microwave-assisted extraction and anion exchange chromatography-inductively coupled plasma mass spectrometry. J. Anal. At. Spectrom. 26: 207. Deutsches Institut fu r Normung and European Committee for Standardization (DIN EN). 2011. Sludge, treated biowaste and soil Digestion of aqua regia soluble fractions of elements. DIN EN 16174. Brussels, Belgium. El-Hadri, F., A. Morales-Rubio, and M. de la Guardia. 2007. Determination of total arsenic in soft drinks by hydride generation atomic uorescence spectrometry. Food Chem. 105: 1196. Fang, K. T. 1994. Uniform Design & Uniform Design Tabulation. Beijing, China: Science Press. GB=T 7485-1987. 1987. Water quality - Determination of total arsenic - Silver diethyldithiocarbamate spectrometric methods. Beijing, China: National Standards of the Peoples Republic of China. General Administration of Quality Supervision, Inspection and Quarantine of the Peoples Republic of China (AQSIQ). 2008. Soil quality-Analysis of total mercury, arsenic and leads contents Atomic uorescence spectrometry Part 2: Analysis of total arsenic contents in soils. GB=T 22105.2-2008. Beijing, China. mez-Ariza, J. L., D. Sa nchez-Rodas, R. Beltra n, W. Corns, and P. Stockwell. 1998. Go Evaluation of atomic uorescence spectrometry as a sensitive detection technique for arsenic speciation. Appl. Organomet. Chem. 12: 439. mez-Ariza, J. L., D. Sa nchez-Rodas, R. Beltra n, and I. Giraldez. 1999. Arsenic Speciation Go in Biological Samples Using the Couplings HPLC-UV-HG-AAS and HPLC-UV-HG-AFS. Int. J. Environ. Anal. Chem. 74: 203. mez-Ariza, J. L., D. Sa nchez-Rodas, I. Giraldez, and E. Morales. 2000a. A comparison Go between ICP-MS and AFS detection for arsenic speciation in environmental samples. Talanta 51: 257. mez-Ariza, J. L., D. Sa nchez-Rodas, I. Gira ldez, and E. Morales. 2000b. Comparison of Go biota sample pretreatments for arsenicspeciation with coupled HPLC-HG-ICP-MS. Analyst 125: 401. Guo, W., S. H. Hu, X. F. Li, J. Zhao, S. S. Jin, W. J. Liu, and H. F. Zhang. 2011. Use of ion molecule reactions and methanol addition to improve arsenic determination in high chlorine food samples by DRC-ICP-MS. Talanta 84: 887. Heilier, J. F., J. P. Buchet, V. Haufroid, and D. Lison. 2005. Comparison of atomic absorption and uorescence spectroscopic methods for the routine determination of urinary arsenic. Int. Arch. Occup. Environ. Health 78: 5159. Husted, S., D. P. Persson, K. H. Laursen, T. H. Hansen, P. Pedas, M. Schiller, J. N. Hegelund, and J. K. Schjoerring. 2011. Review: the role of atomic spectrometry in plant science. J. Anal. At. Spectrom. 26: 5279. Islam, F. S., A. G. Gault, C. Boothman, D. A. Polya, J. M. Charnock, D. Chatterjee, and J. R. Lloyd. 2004. Role of metal-reducing bacteria in arsenic release from Bengal Delta sediments. Nature 430: 68. ISO. 1995. Soil quality - Extraction of trace elements soluble in aqua regia. ISO 11466. Geneva, Switzerland. ISO. 1996. Water quality - Determination of arsenic - Atomic absorption spectrometric method (hydride technique). ISO 11969. Geneva, Switzerland.

Downloaded by [Florida State University] at 18:01 26 March 2013

2506

G. LUO

ISO. 2007. Soil quality - Determination of arsenic, antimony and selenium in aqua regia soil extracts with electrothermal or hydride-generation atomic absorption spectrometry. ISO 20280. Geneva, Switzerland. Ji, Y. B., G. Alaerts, C. J. Xu, Y. Z. Hu, and Y. Vander Heyden. 2006. Sequential uniform designs for ngerprints development of Ginkgo biloba extracts by capillary electrophoresis. J. Chromatogr. A 1128: 273281. Jiang, X. J., W. Gan, S. P. Han, and Y. Z. He. 2008. Determination of Te in soldering tin using continuous owing electrochemical hydride generation atomic uorescence spectrometry. Spectrochim. Acta B 63: 710. Li, R. S., H. T. Yan, X. M. Yang, Z. X. Li, and Y. A. Guo. 2011. Simultaneous determination of trace lead, tin and cadmium in biological samples by a chemical vapor generation-four-channel atomic uorescence spectrometry dual gas-liquid separator system. J. Anal. At. Spectrom. 26: 14901491. Li, Z. X., X. M. Yang, Y. A. Guo, H. T. Li, and Y. H. Feng. 2008. Simultaneous determination of arsenic, antimony, bismuth and mercury in geological materials by vapor generation-four-channel non-dispersive atomic uorescence spectrometry. Talanta 74: 915921. Liang, Y. Z., K. T. Fang, and Q. S. Xu. 2001. Uniform design and its applications in chemistry and chemical engineering. Chemometr. Intell. Lab. 58: 4357. Lindberg, A. L., W. Goessler, M. Grander, B. Nermell, and M. Vahter. 2007. Evaluation of the three most commonly used analytical methods for determination of inorganic arsenic and its metabolites in urine. Toxicol. Lett. 168: 310. Liu, R. S., and Y. J. Tang. 2010. Quantitative analysis for the effect of plant oil and fatty acid on Tuber melanosporum culture by uniform design combined with partial least squares regression. Appl. Microbiol. Biot. 87: 16891697. Liu, Y. S., L. T. Zhang, L. F. Cheng, Q. F. Zeng, W. H. Zhang, W. B. Yang, Z. D. Feng, S. W. Li, and B. Zeng. 2009. Uniform design and regression analysis of LPCVD boron carbide from BCl(3)-CH(4)-H(2) system. Appl. Surf. Sci. 255: 57295735. Loska, K., and D. Wiechula. 2006. Comparison of sample digestion procedures for the determination of arsenic in bottom sediment using hydride generation AAS. Microchim. Acta 154: 235. Lummas, S., J. Ruiz-Jimenez, M. D. L. de Castro, B. Colston, J. Gonzalez-Rodriguez, B. Chen, and W. Corns. 2011. Determination of arsenic, mercury and barium in herbarium mount paper using dynamic ultrasound-assisted extraction prior to atomic uorescence and absorption spectrometry. Anal. Lett. 44: 18421852. Luo, G. B., H. D. Qiu, W. W. Qi, and X. B. Sun. 2005. Simultaneous determination of arsenic and selenium in sewage by hydride generation-atomic uorescence spectrometry. Environ. Prot. Chem. Indus. 25: 247250 (in Chinese). Ministry of Environmental Protection of the Peoples Republic of China (MEP), 1987. Water quality Determination of total arsenic- Silver diethyldithiocarbamate spectrometric methods. GB=T 7485-1987. Beijing, China. Moscoso-Perez, C., J. Moreda-Pineiro, P. Lopez-Mahia, S. Muniategui-Lorenzo, E. Fernandez-Fernandez, and D. Prada-Rodriguez. 2004. Hydride generation atomic uorescence spectrometric determination of As, Bi, Sb, Se(IV) and Te(IV) in aqua regia extracts from atmospheric particulate matter using multivariate optimization. Anal. Chim. Acta 526: 185. Reyes, M. N. M., M. L. Cervera, R. C. Campos, and M. de la Guardia. 2007. Determination of arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid in cereals by hydride generation atomic uorescence spectrometry. Spectrochim. Acta B 62: 1078. Reyes, M. N. M., M. L. Cervera, R. C. Campos, and M. de la Guardia. 2008. Non-chromatographic speciation of toxic arsenic in vegetables by hydride generationatomic uorescence spectrometry after ultrasound-assisted extraction. Talanta 75: 811.

Downloaded by [Florida State University] at 18:01 26 March 2013

DETERMINE TOTAL AS BY AFS WITH TWO CONDITION TESTS

2507

Downloaded by [Florida State University] at 18:01 26 March 2013

nchez-Rodas, D., W. T. Corns, B. Chen, and P. B. Stockwell. 2010. Atomic Fluorescence Sa Spectrometry: a suitable detection technique in speciation studies for arsenic, selenium, antimony and mercury. J. Anal. At. Spectrom. 25: 933935. Shah, A. Q., T. G. Kazi, M. K. Jamali, M. B. Arain, M. K. Jamali, H. I. Afridi, N. Jalbani, G. A. et al 2009. Comparison of electrothermal and hydride generation atomic absorption spectrometry for the determination of total arsenic in broiler chicken. Food Chem. 113: 1351. Tang, Q. Y., and M. G. Feng. 2007. DPS Data processing system: Experimental design, statistical analysis, and data mining. Beijing, China: Science Press. Tang, X. D., Z. R. Xu, and J. H. Wang. 2005. A hydride generation atomic uorescence spectrometric procedure for selenium determination after ow injection on-line co-precipitate preconcentration. Spectrochim. Acta B 60: 1580. Wang, F., and G. Zhang. 2011. Simultaneous quantitative analysis of arsenic, bismuth, selenium, and tellurium in soil samples using multi-channel hydride-generation atomic uorescence spectrometry. Appl. Spectrosc. 65: 315319. Wang, J. H., Y. L. Yu, Z. Du, and Z. L. Fang. 2004. A low cost and sensitive procedure for lead screening in human whole blood with sequential injection-hydride generation-atomic uorescence spectrometry. J. Anal. At. Spectrom. 19: 1559. Wietecha-Posluszny, R., J. Dobrowolska, and P. Koscielniak. 2006. Method for determination of selenium and arsenic in human urine by atomic uorescence spectrometry. Anal. Lett. 39: 27872796. Wu, H., X. C. Wang, B. Liu, Y. L. Liu, S. S. Li, J. S. Lu, J. Y. Tian, W. F. Zhao, and Z. H. Yang. 2011. Simultaneous speciation of inorganic arsenic and antimony in water samples by hydride generation-double channel atomic uorescence spectrometry with on-line solid phase extraction using single-walled carbon nanotubes micro-column. Spectrochim. Acta B 66: 74. Xing, Z., J. Wang, S. C. Zhang, and X. R. Zhang. 2009. Determination of bismuth in solid samples by hydride generation atomic uorescence spectrometry with a dielectric barrier discharge atomizer. Talanta 80: 139. Yong, C. 2000. Speciation and analysis of mercury, arsenic, and selenium by atomic uorescence spectrometry. Trends Anal. Chem. 19: 63. Zhang, N., N. Fu, Z. T. Fang, Y. H. Feng, and L. Ke. 2011. Food Chem. Simultaneous multi-channel hydride generation atomic uorescence spectrometry determination of arsenic, bismuth, tellurium and selenium in tea leaves. Food Chem. 124: 11851188.

Das könnte Ihnen auch gefallen