## 3500-Pb LEAD*

3500-Pb A. Introduction

1. Occurrence and Significance

Lead (Pb) is the fifth element in Group IVA in the periodic table; it has an atomic number of 82, an atomic weight of 207.19, and valences of 2 and 4. The average abundance of Pb in the earth’s crust is 13 ppm; in soils it ranges from 2.6 to 25 ppm; in streams it is 3  g/L, and in groundwaters it is generally  0.1 mg/L. Lead is obtained chiefly from galena (PbS). It is used in batteries, ammunition, solder, piping, pigments, insecticides, and alloys. Lead also was used in gasoline for many years as an anti-knock agent in the form of tetraethyl lead.

The common aqueous species are Pb 2 and hydroxide and carbonate complexes. Lead in a water supply may come fromindustrial, mine, and smelter discharges or from the dissolution of plumbing and plumbing fixtures. Tap waters that are inherently noncorrosive or not suitably treated may contain lead resulting from an attack on lead service pipes, lead interior plumbing, brass fixtures and fittings, or solder pipe joints. Lead is nonessential for plants and animals. It is toxic byingestion and is a cumulative poison. The Food and Drug Administration regulates lead content in food and in house paints. Under the lead-copper rule, the U.S. EPA drinking water 90th percentile action level is 15  g/L.

2. Selection of Method

The atomic absorption spectrometric method (3111B) has a relatively high detection limit in the flame mode and requires an extraction procedure (3111C) for the low concentrationscommon in potable water. The electrothermal atomic absorption (AA) method (3113B) is more sensitive for low concentrations and does not require extraction. The inductively coupled plasma/mass spectrometric method (3125) is even more sensitive than the electrothermal AA method. The inductively coupled plasma method (3120) has a sensitivity similar to that of the flame atomic absorption method. Anodic stripping voltammetry (3130B) can achieve superior detection levels, but is susceptible to interferences from copper, silver, gold,and organic compounds. The dithizone method (B) is sensitive and specific as a colorimetric procedure.



## 3500-Pb B. Dithizone Method

1. General Discussion

a. Principle: An acidified sample containing microgram quantities of lead is mixed with ammoniacal citrate-cyanide reducing solution and extracted with dithizone in chloroform (CHCl 3 ) to form a cherry-red lead dithizonate. The color of the mixed color solution is measured photometrically. 1,2 Sam

ple volume taken for analysis may b e 2 L when digestion is used.

b. Interference: In a weakly ammoniacal cyanide solution (pH 8.5 to 9.5) dithizone forms colored complexes with bismuth, stannous tin, and monovalent thallium. In strongly ammoniacal citrate-cyanide solution (pH 10 to 11.5) the dithizonates of these ions are unstable and are extracted only partially. 3 This methoduses a high pH, mixed color, single dithizone extraction. Interference from stannous tin and monovalent thallium is reducedfurther when these ions are oxidized during preliminary digestion. A modification of the method allows detection and elimination of bismuth interference. Excessive quantities of bismuth, thallium, and tin may be removed. 4

Dithizone in CHCl 3 absorbs at 510 nm; control its interference by using nearly equal concentrations of excess dithizone in samples, standards, and blank. The method is without interference for the determination of 0.0 to 30.0  g Pb in the presence of 20  g Tl , 100  g Sn 2 , 200  g In 3 , and 1000  g each of Ba2 , Cd 2 , Co 2 , Cu 2 , Mg 2 , Mn 2 , Hg 2 , Sr2 , Zn 2 , Al 3 , Sb 3 , As 3 , Cr 3 , Fe 3 , V 3 , PO 4 3

 , and SO 4 2

 . Gram quantities of alkali metals do not interfere. A modification is provided to avoid interference from excessive quantities of bismuth or tin.

c. Preliminary sample treatment: At time of collection acidify with conc HNO 3 to pH  2 but avoid excess HNO 3 . Add 5 mL 0.1 N iodine solution to avoid losses of volatile organo-lead compounds during handling and digesting of samples. Prepare a blank of lead-free water and carry through the procedure.

d. Digestion of samples: Unless digestion is shown to be unnecessary, digest all samples for dissolved or total lead as described in 3030H or K.

e. Minimum detectable concentration: 1.0 g Pb/10 mL dithizone solution.

f. Quality control (QC): The QC practices considered to be an integral part of each method can be found in Section 3020.

2. Apparatus

a. Spectrophotometer for use at 510 nm, providing a light path of 1 cm or longer. * Approved by Standard Methods Committee, 1997. Editorial revisions, 2011. Joint Task Group: 20th Edition—See Section 3500-Al.

1b. pH meter. c. Separatory funnels: 250-mL Squibb type. Clean all glassware, including sample bottles, with 1 1 HNO 3 . Rinse thor

oughly with reagent water.

d. Automatic dispensing burets: Use for all reagents to minimize indeterminate contamination errors.

3. Reagents

Prepare all reagents in lead-free water. a. Stock lead solution: Dissolve 0.1599 g lead nitrate, Pb(NO 3 ) 2 (minimum purity 99.5%), in approximately 200 mL water. Add 10 mL conc HNO 3 and dilute to 1000 mL with water. Alternatively, dissolve 0.1000 g pure Pb metal in 20 mL 1 1 HNO 3 and dilute to 1000 mL with water; 1.00 mL  100  g Pb. b. Working lead solution: Dilute 2.0 mL stock solution to 100 mL with water; 1 mL  2.00  g Pb. c. Nitric acid, HNO 3 , 1 4: Dilute 200 mL conc HNO 3 to 1 L with water.

d. Ammonium hydroxide , NH4 OH, 1 9: Dilute 10 mL conc NH4 OH to 100 mL with water.

e. Citrate-cyanide reducing solution: Dissolve 400 g dibasic ammonium citrate, (NH4) 2HC 6H5 O7 , 20 g anhydrous sodium sul

fite, Na2SO 3 , 10 g hydroxylamine hydrochloride, NH2OH  HCl, and 40 g potassium cyanide, KCN ( CAUTION : Poison) in water and dilute to 1 L. Mix this solution wit h 2 L conc NH4OH. CAUTION : Do not pipet by mouth. Prepare solution in a fume hood.

f. Stock dithizone solution: The dithizone concentration in thestock dithizone solutions is based on having a 100% pure dithizone reagent. Some commercial grades of dithizone are contaminated with the oxidation product diphenylthiocarbodiazone or with metals. Purify dithizone as directed below. For dithizone solutions not stronger than 0.001% (w/v), calculate the exact concentration by dividing the absorbance of the solution in a 1.00-cm cell at 606 nm by 40.6  10 3 , the molar absorptivity.

In a fume hood, dissolve 100 mg dithizone in 50 mL CHCl 3 in a 150-mL beaker and filter through a 7-cm-diam paper.* Receive filtrate in a 500-mL separatory funnel or in a 125-mL erlenmeyer flask under slight vacuum; use a filtering device designed to handle the CHCl 3 vapor. Wash beaker with two 5-mL portions CHCl 3 , and filter. Wash the paper with three 5-mL portions CHCl 3 , adding final portion dropwise to edge of paper. If filtrate is in flask, transfer with CHCl 3 to a 500-mL separatory funnel.

Add 100 mL 1 99 NH4 OH to separatory funnel and shake moderately for 1 min; excessive agitation produces slowly breaking emulsions. Let layers separate, swirling funnel gently to submerge CHCl 3 droplets held on surface of aqueous layer. Transfer CHCl 3 layer to 250-mL separatory funnel, retaining theorange-red aqueous layer in the 500-mL funnel. Repeat extraction, receiving CHCl 3 layer in another 250-mL separatory funnel and transferring aqueous layer, using 1 99 NH4 OH, to the500-mL funnel holding the first extract. Repeat extraction, transferring the aqueous layer to 500-mL funnel. Discard CHCl 3 layer.

To combined extracts in the 500-mL separatory funnel add 1
1 HCl in 2-mL portions, mixing after each addition, untildithizone precipitates and solution is no longer orange-red. Extract precipitated dithizone with three 25-mL portions CHCl 3 . Dilute combined extracts to 1000 mL with CHCl 3 ; 1.00 mL  100  g dithizone. g. Dithizone working solution: Dilute 100 mL stock dithizone solution to 250 mL with CHCl 3 ; 1 mL  40  g dithizone. h. Special dithizone solution: Dissolve 250 mg dithizone in 250 mL CHCl 3 . This solution may be prepared without purifi

cation because all extracts using it are discarded.

i. Sodium sulfite solution: Dissolv e 5 g anhydrous Na2 SO 3 in 100 mL water.

j. Iodine solution: Dissolve 40 g KI in 25 mL water, add 12.7 g resublimed iodine, and dilute to 1000 mL.

4. Procedure

a. With sample digestion: C AUTION : Perform the following procedure (excluding use of spectrophotometer) in a fume hood. To a digested sample containing not more than 1 mL conc acid add 20 mL 1 4 HNO 3 and filter through lead-free filter paper† and filter funnel directly into a 250-mL separatory funnel. Rinse digestion beaker with 50 mL water and add to filter. Add 50 mL ammoniacal citrate-cyanide solution, mix, and cool to room temperature. Add 10 mL dithizone working solution, shake stoppered funnel vigorously for 30 s, and let layers separate. Insert lead-free cotton in stem of separatory funnel and draw off lower layer. Discard 1 to 2 mL CHCl 3 layer, then fill absorption cell. Measure absorbance of extract at 510 nm, using dithizone working solution, 3500-Pb.B.3 g , to zero spectrophotometer.

b. Without sample digestion: To 100 mL acidified sample (pH 2) in a 250-mL separatory funnel add 20 mL 1 4 HNO 3 and50 mL citrate-cyanide reducing solution; mix. Add 10 mL dithizone working solution and proceed as in ¶ a above.

c. Calibration curve: Plot concentration of at least five standards and a blank against absorbance. Determine concentration of lead in extract from curve. All concentrations are  g Pb/10 mL final extract.

d. Removal of excess interferences: The dithizonates of bismuth, tin, and thallium differ from lead dithizonate in maximumabsorbance. Detect their presence by measuring sample absorbance at 510 nm and at 465 nm. Calculate corrected absorbance of sample at each wavelength by subtracting absorbance of blank at same wavelength. Calculate ratio of corrected absorbance at 510 nm to corrected absorbance at 465 nm. The ratio of correctedabsorbances for lead dithizonate is 2.08 and for bismuth dithizonate is 1.07. If the ratio for the sample indicates interference, i.e., is markedly less than 2.08, proceed as follows with a new 100-mL sample: If the sample has not been digested, add 5 mL Na2 SO 3 solution to reduce iodine preservative. Adjust sample to pH 2.5 using a pH meter and 1 4 HNO 3 or 1 9 NH4 OH as required. Transfer sample to 250-mL separatory funnel, extract with a minimum of three 10-mL portions special dithizone solution, or until the CHCl 3 layer is distinctly green. Extract with 20-mL portions CHCl 3 to remove dithizone (absence of green). Add 20 mL 1 4 HNO 3 , 50 mL citrate-cyanide reducing solution, and 10 mL dithizone working solution. Extract as in ¶ 4a and measure absorbance.

* Whatman No. 42, or equivalent. † Whatman No. 541, or equivalent. LEAD (3500-Pb)/Dithizone Method

25. Calculation

mg Pb/L   g Pb (in 10 mL, from calibration curve) mL sample

6. Precision and Bias

Single-operator precision in recovering 0.0104 mg Pb/L from Mississippi River water was 6.8% relative standard deviation and

 1.4% relative error. At the level of 0.026 mg Pb/L, recovery was made with 4.8% relative standard deviation and 15% relative error. 7. References

1. S NYDER , L.J. 1947. Improved dithizone method for determination of

lead—mixed color method at high pH. Anal. Chem. 19:684. 2. S ANDELL , E.B. 1959. Colorimetric Determination of Traces of Metals, 3rd ed. Interscience, New York, N.Y. 3. WICHMANN , H.J. 1939. Isolation and determination of trace metals— the dithizone system. Ind. Eng. Chem. , Anal. Ed. 11:66. 4. AMERICAN S OCIETY FOR TESTING AND M ATERIALS . 1977. Annual Book of ASTM Standards. Part 26, Method D3112-77, American Soc. Testing & Materials, Philadelphia, Pa. LEAD (3500-Pb)/Dithizone Method

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