Nickel

3.6 1.8 5.4 Phosphorus 18 9 27 Selenium 118 (0.5) 18 (0.3) 127 (0.8) Silver 1.7 0.9 2.6 Thallium 19.6 (0.2) 14.8 (0.1) 114.4 (0.3) Zinc 0.5 0.3 0.8 Mercury analysis only. Detection limit when analyzed by GFAAS. 2 Detection limit when analyzed by CVAAS, estimated for Back-Half and Total Train. See Sections 2.2 and 5.4.3. Note: Actual method In-stack detection limits may vary from these values, as described in Section 2.3.3. 2.3.2 To ensure optimum precision/resolution in the analyses, the target concentrations of metals in the analytical solutions should be at least ten times their respective analytical detection limits. Under certain conditions, and with greater care in the analytical procedure. these concentrations can be as low as approximately three times the respective analytical detection limits without seriously impairing the precision of the analyses. On at least one sample run in the source test, and for each metal analyzed, perform either repetitive analyses, Method of Standard Additions, serial dilution, or matrix spike addition, etc., to document the quality of the data. 2.3.3 Actual In-stack method detection limits are based on actual source sampling parameters and analytical results as described above. If required, the method instack detection limits can be improved over those shown in Table 29-1 for a specific test by either increasing the sampled stack gas volume, reducing the total volume of the digested samples, improving the analytical detection limits, or any combination of the three. For extremely low levels of Hg only. the aliquot size selected for digestion and analysis can be increased to as much as 10 ml. thus Improving the in-stack detection limit by a factor of ten compared to a 1 ml aliquot size. 2.3.3.1 A nominal one hour sampling run will collect a stack gas sampling volume of about 1.25 m3. If the sampling time is increased to four hours and 5 m 3 are collected. the in-stack method detection limits would be Improved by a factor of four compared to the values shown in Table 29-1. 2.3.3.2 The In-stack detection limits assume that all of the sample is digested and the final liquid volumes for analysis are the normal values of 300 ml for Analytical Fraction 1. and 150 ml for Analytical Fraction 2A. If the volume of Analytical Fraction 1 is reduced from 300 to 30 ml. the in-stack detection limits for that fraction of the sample would be Improved by a factor of ten. If the volume of Analytical Fraction 2A is reduced from 150 to 25 ml. the in-stack detection Iimits for that fraction of the sample would be improved by a factor of six. Matrix effect checks are necessary on sample analyses and typically are of much greater significance for samples that have been concentrated to Environmental Protection Agency, EPA less than the normal original sample volume. Reduction of Analytical Fractions 1 and 2A to volumes of less than 30 and 25 ml. respectively, could Interfere with the redissolving of the residue and could increase interference by other compounds to an intolerable level. 2.3.3.3 When both of the modifications described in Sections 2.3.3.1 and 2.3.3.2 are used simultaneously on one sample. the resultant Improvements are multiplicative. For example. an increase in stack gas volume by a factor of four and a reduction in the total liquid sample digested volume of both Analytical Fractions 1 and 2A by a factor of six would result in an improvement by a factor of twenty-four of the in-stack method detection limit. 2.4 Precision. The precision (relative standard deviation) for each metal detected in a method development test performed at a sewage sludge incinerator were found to be as follows: Sb (12.7 percent). As (13.5 percent), Ba (20.6 percent), Cd (11.5 percent), Cr (11.2 percent), Cu (11.5 percent), Pb (11.6 percent), P (14.6 percent), Se (15.3 percent). TI (12.3 percent). and Zn (11.8 percent). The precision for Ni was 7.7 percent for another test conducted at a source simulator. Be, Mn. and Ag were not detected in the tests. However, based on the analytical detection limits of the ICAP for these metals, their precisions could be similar to those for the other metals when detected at similar levels. 2.5 Interferences. Iron (Fe) can be a spectral interference during the analysis of As, Cr, and Cd by ICAP. Aluminum (Al) can be a spectral interference during the analysis of As and Pb by ICAP. Generally, these interferences can be reduced by diluting the analytical sample. but such dilution raises the in-stack detection limits. Background and overlap corrections may be used to adjust for spectral interferences. Refer to Method 6010 in EPA Publication SW-846 Third Edition (November 1986) including updates I, II, IIA and IIB, as incorporated by reference in $60.17(i) the other analytical methods used for details on potential interferences to this method. For all GFAAS analyses, use matrix modifiers to limit Interferences, and matrix match all standards. 3. Apparatus 3.1 Sampling. A schematic of the sampling train is shown In Figure 29-1. It has general similarities to the Method 5 train. ER25AP96.000 3.1.1 Probe Nozzle (Probe Tip) and Borosilicate or Quartz Glass Probe Liner. Same as Method 5. Sections 2.1.1 and 2.1.2. except that glass nozzles are required unless alternate tips are constructed of materials that are free from contamination and will not interfere with the sample. If a probe tip other than glass is used. no correction to the Environmental Protection Agency, EPA sample test results to compensate for the nozzle's effect on the sample is allowed. Probe fittings of plastic such as Teflon, polypropylene, etc. are recommended instead of metal fittings to prevent contamination. If one chooses to do so, a single glass piece consisting of a combined probe tip and probe liner may be used. 3.1.2 Pitot Tube and Differential Pressure Gauge. Same as Method 2, Sections 2.1 and 2.2, respectively. 3.1.3 Filter Holder. Glass, same as Method 5. Section 2.1.5, except use a Teflon filter support or other non-metallic, non-contaminating support in place of the glass frit. 3.1.4 Filter Heating System. Same as Method 5, Section 2.1.6. 3.1.5 Condenser. Use the following system for condensing and collecting gaseous metals and determining the moisture content of the stack gas. The condensing system shall consist of four to seven impingers connected in series with leak-free ground glass fittings or other leak-free, non-contaminating fittings. Use the first impinger as a moisture trap. The second impinger (which is the first HNO₃/H₂O₂ impinger) shall be identical to the first impinger in Method 5. The third Impinger (which is the second HNO₃/H₂ O₂ Impinger) shall be a Greenburg Smith impinger with the standard tip as described for the second impinger in Method 5, Section 2.1.7. The fourth (empty) impinger and the fifth and sixth (both acidified KMnO4 ) impingers are the same as the first impinger in Method 5. Place a thermometer capable of measuring to within 1 °C (2 °F) at the outlet of the last impinger. If no Hg analysis is planned, then the fourth, fifth, and sixth impingers are not used. 3.1.6 Metering System, Barometer, and Gas Density Determination Equipment. Same as Method 5, Sections 2.1.8 through 2.1.10, respectively. 3.1.7 Teflon Tape. For capping openings and sealing connections. If necessary, on the sampling train. 3.2. Sample Recovery. Same as Method 5, Sections 2.2.1 through 2.2.8 (Probe-Liner and Probe-Nozzle Brushes or Swabs. Wash Bottles, Sample Storage Containers, Petri Dishes, Glass Graduated Cylinder, Plastic Storage Containers, Funnel and Rubber Policeman. and Glass Funnel), respectively, with the following exceptions and additions: 3.2.1 Non-metallic Probe-Liner and Probe- Nozzle Brushes or Swabs. Use non-metallic probe-liner and probe-nozzle brushes or swabs for quantitative recovery of materials collected in the front-half of the sampling train. 3.2.2 Sample Storage Containers. Use glass bottles (see the Precaution: in Section 4.3.2 of this Method) with Teflon-lined caps that are non-reactive to the oxidizing solutions, with capacities of 1000- and 500-ml, for storage of acidified KMnO4- containing samples and blanks. Glass or polyethylene bottles may be used for other sample types. 3.2.3 Graduated Cylinder. Glass or equivalent. 3.2.4 Funnel. Glass or equivalent. 3.2.5 Labels. For identifying samples. 3.2.6 Polypropylene Tweezers and/or Plastic Gloves. For recovery of the filter from the sampling train filter holder. 3.3 Sample Preparation and Analysis. 3.3.1 Volumetric Flasks, 100-ml, 250-ml, and 100-ml. For preparation of standards and sample dilutions. 3.3.2 Graduated Cylinders. For preparation of reagents. 3.3.3 Parr Bombs or Microwave Pressure Relief Vessels with Capping Station (CEM Corporation model or equivalent). For sample digestion. 3.3.4 Beakers and Watch Glasses. 250-ml beakers, with watch glass covers, for sample digestion. 3.3.5 Ring Stands and Clamps. For securing equipment such as filtration apparatus. 3.3.6 Filter Funnels. For holding filter paper. 3.3.7 Disposable Pasteur Pipets and Bulbs. 3.3.8 Volumetric Pipets. 3.3.9 Analytical Balance. Accurate to within .01 mg. 3.3.10 Microwave or Conventional Oven. For heating samples at fixed power levels or temperatures, respectively. 3.3.11 Hot Plates. 3.3.12 Atomic Absorption Spectrometer (AAS). Equipped with a background corrector. 3.3.12.1 Graphite Furnace Attachment. With Sb. As, Cd. Co. Pb, Se, and TI hollow cathode lamps (HCLs) or electrodeless discharge lamps (EDLs). Same as Methods 7041 (Sb), 7060 (As), 7131 (Cd). 7201 (Co), 7421 (Pb), 7740 (Se), and 7841 (TI) in EPA publication SW-846 Third Edition (November 1886) including updates I, II, IIA and IIB, as incorporated by reference in $60.17(i). 3.3.12.2 Cold Vapor Mercury Attachment. With a mercury HCL or EDL, an air recirculation pump, a quartz cell, an aerator apparatus, and a heat lamp or desiccator tube. The heat lamp shall be capable of raising the temperature at the quartz cell by 10 °C above ambient. so that no condensation forms on the wall of the quartz cell. Same as Method 6020 in EPA publication SW-846 Third Edition (November 1986) including updates I. II, IIA and IIB, as incorporated by reference in $60.17(i). See NOTE No. 2: Section 5.4.3 for other acceptable approaches for analysis of Hg in which analytical detection limits of 0.002 ng/ml were obtained. 3.3.13 Inductively Coupled Argon Plasma Spectrometer. With either a direct or sequential reader and an alumina torch. Same as EPA Method 6010 in EPA publication SW- 846 Third Edition (November 1986) including Pt. 60, App. A, Meth. 29 updates I, II. IIA and IIB, as Incorporated by reference in $60.17(i). 3.3.14 Inductively Coupled Plasma-Mass Spectrometer. Same as EPA Method 6020 in EPA publication SW-846 Third Edition (November 1986) including updates I. II, IIA and ПВ, as incorporated by reference in $60.17(i). d. Reagents 4.1 Unless otherwise indicated, it is intended that all reagents conform to the specifications established by the Committee on Analytical Reagents of the American Chemical Society, where such specifications are available. Otherwise. use the best available grade. 4.2 Sampling Reagents. 4.2.1 Sample Filters. Without organic binders. The filters shall contain less than 1.3 µg/In.² of each of the metals to be measured. Analytical results provided by filter manufacturers stating metals content of the filters are acceptable. However, If no such results are available, analyze filter blanks for each target metal prior to emission testing. Quartz fiber filters meeting these requirements are recommended. However, if glass fiber filters become available which meet these requirements, they may be used. Filter efficiencies and unreactiveness to sulfur dioxide (SO₂) or sulfur trioxide (SO 3) shall be as described in Section 3.1.1 of Method 5. 4.2.2 Water. To conform to ASTM Specification D1193-77, Type II (incorporated by reference-See $60.17). If necessary, analyze the water for all target metals prior to field use. All target metals should be less than 1 ng/ml. 4.2.3 Nitric Acid (HNO₂). Concentrated. Baker Instra-analyzed or equivalent. 4.2.4 Hydrochloric Acid (HCL). Concentrated. Baker Instra-analyzed or equivalent. 4.2.5 Hydrogen Peroxide (H₂O₂), 30 Percent (V/V). 4.2.6 Potassium Permanganate (KMnO4 ). 4.2.7 Sulfuric Acid (H2SO4). Concentrated. 4.2.8 Silica Gel and Crushed Ice. Same as Method 5, Sections 3.1.2 and 3.1.4. respectively. 4.3 Pretest Preparation of Sampling Reagents. 4.3.1 Absorbing Solution, 5 Percent HNO3/10 Percent H₂O₂. Add carefully with stirring 50 ml of concentrated HNO3 to a 1000-ml volumeric flask containing approximately 500 ml of water, and then add carefully with stirring 333 ml of 30 percent H2O2. Dilute to volume with water. Mix well. This reagent shall contain less than 2 ng/ml of each target metal. 4.3.2 Acidic KMnO4 Absorbing Solution, 4 Percent KMnO₄ (W/V). 10 Percent H2SO4 (V/ V). Prepare fresh daily. Mix carefully. with stirring, 100 ml of concentrated H2SO4 into approximately 800 ml of water. and add water with stirring to make a volume of 1 liter: this solution is 10 percent H2SO4 (V/V). Dissolve, with stirring, 40 g of KMnO4 into 10 percent H₂ SO4 (V/V) and add 10 percent H2SO4 (V/V) with stirring to make a volume of 1 liter. Prepare and store in glass bottles to prevent degradation. This reagent shall contain less than 2 ng/ml of Hg. Precaution: To prevent autocatalytic decomposition of the permanganate solution, filter the solution through Whatman 541 filter paper. Also. due to the potential reaction of the potassium permanganate with the acid, there could be pressure buildup in the solution storage bottle. Therefore these bottles shall not be fully filled and shall be vented to relieve excess pressure and prevent explosion potentials. Venting is required, but not in a manner that will allow contamination of the solution. A No. 70-72 hole drilled in the container cap and Teflon liner has been used. 4.3.3 HNO3, 0.1 N. Add with stirring 6.3 ml of concentrated HNO3 (70 percent) to a flask containing approximately 900 ml of water. Dilute to 1000 ml with water. Mix well. This reagent shall contain less than 2 ng/ml of each target metal. 4.3.4 HCI, 8 N. Carefully add with stirring 690 ml of concentrated HCI to a flask containing 250 ml of water. Dilute to 1000 ml with water. Mix well. This reagent shall contain less than 2 ng/ml of Hg. 4.4 Glassware Cleaning Reagents. 4.4.1 HNO3. Concentrated. Fisher ACS grade or equivalent. 4.4.2 Water. To conform to ASTM Specification D1193-77, Type II (incorporated by reference-See $60.17). 4.4.3 HNO3, 10 Percent (V/V). Add with stirring 500 ml of concentrated HNO3 to a flask containing approximately 4000 ml of water. Dilute to 5000 ml with water. Mix well. This reagent shall contain less than 2 ng/ml of each target metal. 4.5 Sample Digestion and Analysis Reagents. The metals standards, except Hg, may also be made from solid chemicals as described in Citation 3 of the Bibliography. Refer to Citations 1. 2. or 5 of the Bibliography for additional information on Hg standards. The 1000 µg/ml Hg stock solution standard may be made according to Section 6.2.5 of Method 101A. 4.5.1 HCL. Concentrated. 4.5.2 Hydrofluoric Acid (HF), Concentrated. 4.5.3 HNO3. Concentrated. Baker Instraanalyzed or equivalent. 4.5.4 HNO3. 50 Percent (V/V). Add with stirring 125 ml of concentrated HNO3 to 100 ml of water. Dilute to 250 ml with water. Mix well. This reagent shall contain less than 2 ng/ml of each target metal. 4.5.5 HNO3, 5 Percent (V/V). Add with stirring 50 ml of concentrated HNO3 to 800 ml of water. Dilute to 1000 ml with water. Mix Environmental Protection Agency, EPA well. This reagent shall contain less than 2 ng/ml of each target metal. 4.5.6 Water. To conform to ASTM Specification D1193-77, Type II (incorporated by reference-See $60.17). 4.5.7 Hydroxylamine Hydrochloride and Sodium Chloride Solution. See Citation 2 of the Bibliography for preparation. 4.5.8 Stannous Chloride. See Citation 2 of the Bibliography for preparation. 4.5.9 KMnO4, 5 Percent (W/V). See Citation 2 of the Bibliography for preparation. 4.5.10 H2SO4. Concentrated. 4.5.11 Potassium Persulfate, 5 Percent (W/ V). See Citation 2 of the Bibliography for preparation. 4.5.12 Nickel Nitrate, NI (NO₃ )₂ 6H₂O. 4.5.13 Lanthanum Oxide. Laz O3. 4.5.14 Hg Standard (AAS Grade), 1000 µg/ ml. 4.5.15 Pb Standard (AAS Grade), 1000 µg/ ml. 4.5.16 As Standard (AAS Grade), 1000 µg/ ml. 4.5.17 Cd Standard (AAS Grade), 1000 µg/ ml. 4.5.18 Cr Standard (AAS Grade), 1000 µg/ ml. 4.5.19 Sb Standard (AAS Grade), 1000 µg/ ml. 4.5.20 Ba Standard (AAS Grade), 1000 µg/ ml. 4.5.21 Be Standard (AAS Grade), 1000 µg/ ml. 4.5.22 Co Standard (AAS Grade), 1000 µg/ ml. ml. 4.5.28 Ag Standard (AAS Grade), 1000 µg/ ml. 4.5.29 TI Standard (AAS Grade). 1000 µg/ ml. 4.5.30 Zn Standard (AAS Grade). 1000 µg/ ml. 4.5.31 AI Standard (AAS Grade), 1000 µg/ ml. 4.5.32 Fe Standard (AAS Grade), 1000 µg/ ml. 4.5.23 Cu Standard (AAS Grade). 1000 µg/ ml. 4.5.24 Mn Standard (AAS Grade), 1000 µg/ ml. 4.5.25 Ni Standard (AAS Grade), 1000 µg/ 4.5.26 P Standard (AAS Grade), 1000 µg/ml. 4.5.27 Se Standard (AAS Grade). 1000 µg/ ml. 4.5.33 Hg Standards and Quality Control Samples. Prepare fresh weekly a 10 µg/ml intermediate Hg standard by adding 5 ml of 1000 µg/ml Hg stock solution prepared according to Method 101A to a 500-ml volumetric flask; dilute with stirring to 500 ml by first carefully adding 20 ml of 15 percent HNO3 and then adding water to the 500-ml volume. Mix well. Prepare a 200 ng/ml working Hg standard solution fresh daily: add 5 ml of the 10 µg/ml Intermediate standard to a 250-ml volumetric flask, and dilute to 250 ml with 5 ml of 4 percent KMnO4. 5 ml of 15 percent HNO3. and then water. Mix well. Use at least five separate aliquots of the working Hg standard solution and a blank to prepare the standard curve. These aliquots and blank shall contain 0.0, 1.0, 2.0, 3.0, 4.0. and 5.0 ml of the working standard solution containing 0. 200, 400, 600, 800, and 1000 ng Hg, respectively. Prepare quality control samples by making a separate 10 µg/ml standard and diluting until in the calibration range. 4.5.34 ICAP Standards and Quality Control Samples. Calibration standards for ICAP analysis can be combined into four different mixed standard solutions as follows: MIXED STANDARD SOLUTIONS FOR ICAP ANALYSIS Solution Elements I As, Be, Cd, Mn. Pb, Se, Zn. u Ba, Co, Cu, Fe. m AI, Cr, NI. IV Ag, P, Sb, TL Prepare these standards by combining and diluting the appropriate volumes of the 1000 µg/ml solutions with 5 percent HNO3. A minimum of one standard and a blank can be used to form each calibration curve. However, prepare a separate quality control sample spiked with known amounts of the target metals in quantities In the mid-range of the calibration curve. Suggested standard levels are 25 µg/ml for Al. Cr and Pb. 15 µg/ml for Fe, and 10 µg/ml for the remaining elements. Prepare any standards containing less than 1 µg/ml of metal on a daily basis. Standards containing greater than 1 µg/ml of metal should be stable for a minimum of 1 to 2 weeks. For ICP-MS. follow Method 6020 in EPA Publication SW-846 Third Edition (November 1986) including updates I, II, IIA and IIB, as incorporated by reference in $60.17(i). 4.5.35 GFAAS Standards. Sb, As, Cd, Co, Pb, Se, and TI. Prepare a 10 µg/ml standard by adding 1 ml of 1000 µg/ml standard to a 100-ml volumetric flask. Dilute with stirring to 100 ml with 10 percent HNO3. For GFAAS, matrix match the standards. Prepare a 100 ng/ml standard by adding 1 ml of the 10 µg/ml standard to a 100-ml volumetric flask, and dilute to 100 ml with the appropriate matrix solution. Prepare other standards by diluting the 100 ng/ml standards. Use at least five standards to make up the standard curve. Suggested levels are 0. 10. 50. 75. and 100 ng/ ml. Prepare quality control samples by making a separate 10 µg/ml standard and diluting until it is in the range of the samples. Prepare any standards containing less than 1 µg/ ml of metal on a daily basis. Standards containing greater than 1 µg/ml of metal should be stable for a minimum of I to 2 weeks. 4.5.36 Matrix Modifiers. 4.5.36.1 Nickel Nitrate, 1 Percent (V/V). Dissolve 4.956 g of Ni or Pt. 60, App. A, Meth. 29 other nickel compound suitable for preparation of this matrix modifier in approximately 50 ml of water in a 100-ml volumetric flask. Dilute to 100 ml with water. 4.5.36.2 Nickel Nitrate, 0.1 Percent (V/V). Dilute 10 ml of 1 percent nickel nitrate solution to 100 ml with water. Inject an equal amount of sample and this modifier into the graphite furnace during GFAAS analysis for As. 4.5.36.3 Lanthanum. Carefully dissolve 0.5864 g of La2 O3 in 10 ml of concentrated HNO3, and dilute the solution by adding It with stirring to approximately 50 ml of water. Dilute to 100 ml with water, and mix well. Inject an equal amount of sample and this modifier into the graphite furnace during GFAAS analysis for Pb. 4.5.37 Whatman 40 and 541 Filter Papers (or equivalent). For filtration of digested samples. 5. Procedure 5.1 Sampling. The complexity of this method is such that, to obtain reliable results, both testers and analysts must be trained and experienced with the test procedures, including source sampling: reagent preparation and handling; sample handling: safety equipment and procedures: analytical calculations; reporting: and the specific procedural descriptions throughout this method. 5.1.1 Pretest Preparation. Follow the same general procedure given in Method 5,