ALUMINUM (3500-Al)/Introduction

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3500-Al ALUMINUM*

3500-Al A. Introduction
1. Occurrence and Signicance

Aluminum (Al) is the second element in Group IIIA of the periodic table; it has an atomic number of 13, an atomic weight of 26.98, and a valence of 3. The average abundance in the earths crust is 8.1%; in soils it is 0.9 to 6.5%; in streams it is 400 g/L; in U.S. drinking waters it is 54 g/L, and in groundwater it is 0.1 g/L. Aluminum occurs in the earths crust in combination with silicon and oxygen to formfeldspars, micas, and clay minerals. The most important minerals are bauxite and corundum, which is used as an abrasive. Aluminum and its alloys are used for heat exchangers, aircraft parts, building materials, containers, etc. Aluminum potassium sulfate (alum) is used in water-treatment processes to occulate suspended particles, but it may leave a residue of aluminum in the nished water.

Aluminums occurrence in natural waters is controlled by pH and by very nely suspended mineral particles. The cation Al3 predominates at pH less than 4. Above neutral pH, the predominant dissolved form is Al(OH)4. Aluminum is nonessential for plants and animals. Concentrations exceeding 1.5 mg/L constitute a toxicity hazard in the marine environment, and levels below 200 g/L present a minimal risk. The United Nations Food and Agriculture Organizations recommended maximum level for irrigation waters is 5 mg/L. The possibility of a link between elevated aluminum levels in brain tissues and Alzheimers disease has been raised. The U.S. EPA secondary drinking water regulations list an optimal secondary maximum contaminant level (SMCL) of 0.05 mg/L and maximum SMCL of 0.2 mg/L.
2. Selection of Method

* Approved by Standard Methods Committee, 2001. Joint Task Group: 20th EditionBrian J. Condike (chair), Deanna K. Anderson, Anthony Bright, Richard A. Cahill, Alois F. Clary, C. Ellen Gonter, Peter M. Grohse, Daniel C. Hillman, Albert C. Holler, Amy Hughes, J. Charles Jennett, Roger A. Minear, Marlene O. Moore, Gregg L. Oelker, S. Kusum Perera, James G. Poff, Jeffrey G. Skousen, Michael D. Wichman, John L. Wuepper.

The atomic absorption spectrometric methods (3111D and E, and 3113B) and the inductively coupled plasma methods (3120 and 3125) are free from such common interferences as uoride and phosphate, and are preferred. The Eriochrome cyanine R colorimetric method (B) provides a means for estimating aluminum with simpler instrumentation.

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3500-Al B. Eriochrome Cyanine R Method

1. General Discussion

a. Principle: With Eriochrome cyanine R dye, dilute aluminum solutions buffered to a pH of 6.0 produce a red to pink complex that exhibits maximum absorption at 535 nm. The intensity of the developed color is inuenced by the aluminum concentration, reaction time, temperature, pH, alkalinity, and concentration of other ions in the sample. To compensate for color and turbidity, the aluminum in one portion of sample is complexed with EDTA to provide a blank. The interference of iron and manganese, two elements commonly found in water when aluminum is present, is eliminated by adding ascorbic acid. The optimum aluminum range lies between 20 and 300 g/L but can be extended upward by sample dilution. b. Interference: Negative errors are caused by both uoride and polyphosphates. When the uoride concentration is constant, the percentage error decreases with increasing amounts of aluminum. Because the uoride concentration often is known or can be determined readily, fairly accurate results can be obtained by adding the known amount of uoride to a set of standards. A simpler correction can be determined from the family of curves in Figure 3500-Al:1. A procedure is given for the removal of complex phosphate interference. Orthophosphate in concentrations under 10 mg/L does not interfere. The interference caused by even small amounts of alkalinity is removed by acidifying the sample just beyond the neutralization point of methyl orange. Sulfate does not interfere up to a concentration of 2000 mg/L. c. Minimum detectable concentration: The minimum aluminum concentration detectable by this method in the absence of uorides and complex phosphates is approximately 6 g/L. d. Sample handling: Collect samples in clean, acid-rinsed bottles, preferably plastic, and examine them as soon as possible after collection. If only soluble aluminum is to be determined, lter a portion of sample through a 0.45-m membrane lter; discard rst 50 mL of ltrate and use succeeding ltrate for the determination. Do not use lter paper, absorbent cotton, or glass wool for ltering any solution that is to be tested for aluminum, because they will remove most of the soluble aluminum.
2. Apparatus

a. Colorimetric equipment: One of the following is required: 1) Spectrophotometer, for use at 535 nm, with a light path of 1 cm or longer. 2) Filter photometer, providing a light path of 1 cm or longer and equipped with a green lter with maximum transmittance between 525 and 535 nm. 3) Nessler tubes, 50-mL, tall form, matched. b. Glassware: Treat all glassware with warm 1 1 HCl and rinse with aluminum-free distilled water to avoid errors due to materials absorbed on the glass. Rinse sufciently to remove all acid.
3. Reagents

a. Stock aluminum solution: Use either the metal (1) or the salt (2) for preparing stock solution; 1.00 mL 500 g Al: 1) Dissolve 500.0 mg aluminum metal in 10 mL conc HCl by heating gently. Dilute to 1000 mL with water, or 2) Dissolve 8.791 g aluminum potassium sulfate (also called potassium alum), AlK(SO4)2 12H2O, in water and dilute to 1000 mL. Correct this weight by dividing by the decimal fraction of assayed AlK(SO4)2 12H2O in the reagent used. b. Standard aluminum solution: Dilute 10.00 mL stock aluminum solution to 1000 mL with water; 1.00 mL 5.00 g Al. Prepare daily. c. Sulfuric acid, H2SO4, 0.02N and 6N. d. Ascorbic acid solution: Dissolve 0.1 g ascorbic acid in water and make up to 100 mL in a volumetric ask. Prepare fresh daily. e. Buffer reagent: Dissolve 136 g sodium acetate, NaC2H3O2 3H2O, in water, add 40 mL 1N acetic acid, and dilute to 1 L. f. Stock dye solution: Use any of the following products: 1) Solochrome cyanine R-200* or Eriochrome cyanine: Dissolve 100 mg in water and dilute to 100 mL in a volumetric ask. This solution should have a pH of about 2.9. 2) Eriochrome cyanine R: Dissolve 300 mg dye in about 50 mL water. Adjust pH from about 9 to about 2.9 with 1 1 acetic acid (approximately 3 mL will be required). Dilute with water to 100 mL. 3) Eriochrome cyanine R: Dissolve 150 mg in about 50 mL water. Adjust pH from about 9 to about 2.9 with 1 1 acetic acid (approximately 2 mL will be required). Dilute with water to 100 mL. Stock solutions have excellent stability and can be kept for at least a year. g. Working dye solution: Dilute 10.0 mL of selected stock dye solution to 100 mL in a volumetric ask with water. Working solutions are stable for at least 6 months. h. Methyl orange indicator solution, or bromcresol green indicator solution specied in the total alkalinity determination (Section 2320B.3d). i. EDTA (sodium salt of ethylenediamine-tetraacetic acid dihydrate), 0.01M: Dissolve 3.7 g in water, and dilute to 1 L. j. Sodium hydroxide, NaOH, 1N and 0.1N.
4. Procedure

a. Preparation of calibration curve: 1) Prepare a series of aluminum standards from 0 to 7 g (0 to 280 g/L based on a 25-mL sample) by accurately measuring the calculated volumes of standard aluminum solution into 50-mL volumetric asks or nessler tubes. Add water to a total volume of approximately 25 mL. 2) Add 1 mL 0.02N H2SO4 to each standard and mix. Add 1 mL ascorbic acid solution and mix. Add 10 mL buffer solution
* Arnold Hoffman & Co., Providence, RI. K & K Laboratories, K & K Lab. Div., Life Sciences Group, Plainview, NY. Pfaltz & Bauer, Inc., Stamford, CT. EM Science, Gibbstown, NJ.

Use reagents low in aluminum, and aluminum-free distilled water.

ALUMINUM (3500-Al)/Eriochrome Cyanine R Method

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Figure 3500-Al:1. Correction curves for estimation of aluminum in the presence of uoride. Above the mg F/L present, locate the point corresponding to the apparent mg Al/L measured. From this point interpolate between the curves shown, if the point does not fall directly on one of the curves, to read the true mg Al/L on the ordinate, which corresponds to 0.00 mg F/L. For example, an apparent 0.20 mg Al/L in a sample containing 1.00 mg F/L would actually be 0.30 mg Al/L if no uoride were present to interfere.

and mix. With a volumetric pipet, add 5.00 mL working dye reagent and mix. Immediately make up to 50 mL with distilled water. Mix and let stand for 5 to 10 min. The color begins to fade after 15 min. 3) Read transmittance or absorbance on a spectrophotometer, using a wavelength of 535 nm or a green lter providing maximum transmittance between 525 and 535 nm. Adjust instrument to zero absorbance with the standard containing no aluminum. Plot concentration of Al (micrograms Al in 50 mL nal volume) against absorbance.

b. Sample treatment in absence of uoride and complex phosphates: Place 25.0 mL sample, or a portion diluted to 25 mL, in a porcelain dish or ask, add a few drops of methyl orange indicator, and titrate with 0.02N H2SO4 to a faint pink color. Record reading and discard sample. To two similar samples at room temperature add the same amount of 0.02N H2SO4 used in the titration and 1 mL in excess. To one sample add 1 mL EDTA solution. This will serve as a blank by complexing any aluminum present and compensating for color and turbidity. To both samples add 1 mL ascorbic acid,

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10 mL buffer reagent, and 5.00 mL working dye reagent as prescribed in a2) above. Set instrument to zero absorbance or 100% transmittance using the EDTA blank. After 5 to 10 min contact time, read transmittance or absorbance and determine aluminum concentration from the calibration curve previously prepared. c. Visual comparison: If photometric equipment is not available, prepare and treat standards and a sample, as described above, in 50-mL nessler tubes. Make up to mark with water and compare sample color with the standards after 5 to 10 min contact time. A sample treated with EDTA is not needed when nessler tubes are used. If the sample contains turbidity or color, the use of nessler tubes may result in considerable error. d. Removal of phosphate interference: Add 1.7 mL 6N H2SO4 to 100 mL sample in a 200-mL erlenmeyer ask. Heat on a hot plate for at least 90 min, keeping solution temperature just below the boiling point. At the end of the heating period solution volume should be about 25 mL. Add water if necessary to keep it at or above that volume. After cooling, neutralize to a pH of 4.3 to 4.5 with NaOH, using 1N NaOH at the start and 0.1N for the nal ne adjustment. Monitor with a pH meter. Make up to 100 mL with water, mix, and use a 25-mL portion for the aluminum test. Run a blank in the same manner, using 100 mL distilled water and 1.7 mL 6N H2SO4. Subtract blank reading from sample reading or use it to set instrument to zero absorbance before reading the sample. e. Correction for samples containing uoride: Measure sample uoride concentration by the SPADNS or electrode method. Either: 1) Add the same amount of uoride as in the sample to each aluminum standard, or 2) Determine uoride correction from the set of curves in Figure 3500-Al:1.
5. Calculation
mg Al/L

6. Precision and Bias

A synthetic sample containing 520 g Al/L and no interference in distilled water was analyzed by the Eriochrome cyanine R method in 27 laboratories. Relative standard deviation was 34.4% and relative error 1.7%. A second synthetic sample containing 50 g Al/L, 500 g Ba/L, and 5 g Be/L in distilled water was analyzed in 35 laboratories. Relative standard deviation was 38.5% and relative error 22.0%. A third synthetic sample containing 500 g Al/L, 50 g Cd/L, 110 g Cr/L, 1000 g Cu/L, 300 g Fe/L, 70 g Pb/L, 50 g Mn/L, 150 g Ag/L, and 650 g Zn/L in distilled water was analyzed in 26 laboratories. Relative standard deviation was 28.8% and relative error 6.2%. A fourth synthetic sample containing 540 g Al/L and 2.5 mg polyphosphate/L in distilled water was analyzed in 16 laboratories that hydrolyzed the sample in the prescribed manner. Relative standard deviation was 44.3% and relative error 1.3%. In 12 laboratories that applied no corrective measures, the relative standard deviation was 49.2% and the relative error 8.9%. A fth synthetic sample containing 480 g Al/L and 750 g F/L in distilled water was analyzed in 16 laboratories that relied on the curve to correct for the uoride content. Relative standard deviation was 25.5% and relative error 2.3%. The 17 laboratories that added uoride to the aluminum standards showed a relative standard deviation of 22.5% and a relative error of 7.1%.

7. Bibliography
SHULL, K.E. & G.R. GUTHAN. 1967. Rapid modied Eriochrome cyanine R method for determination of aluminum in water. J. Amer. Water Works Assoc. 59:1456.

g Al (in 50 mL final volume) mL sample