Analysis of Trace and Non-Trace Elements in Waters and Wastes by EPA Method 200.

Written by: Eric D. Dodds Approved by: Dr. John M. Kennish Applied Science, Engineering, and Technology Laboratory University of Alaska Anchorage Revised: by Birgit Hagedorn November 2007 Analysis of Trace and Non-Trace Elements in Waters and Wastes by EPA Method 200.8

Analysis of Elements by EPA 200.8

Application and Methodology Based on EPA method 200.8, the analytical methods described here allow for the quantitaion of dissolved or total elements in samples such as ground waters, surface waters, and drinking water. Total recoverable elements in waste waters, sludges, and soils may also be determined. Analysis of appropriately prepared samples is conducted by inductively coupled plasma mass spectrometry (ICP-MS). The analytes shown in Table I constitute the usual suite of trace elements included in method 200.8 analyses; however, additional nontrace elements (such as calcium, iron, magnesium, potassium, sodium) may be determined in aqueous matrices as appropriate.
Table I. Typical suite of elements determined by EPA Method 200.8. Element Name Element Symbol Aluminum Al Antimony Sb Arsenic As Barium Ba Beryllium Be Cadmium Cd Chromium Cr Trace Elements Cobalt Co EPA 200.8 Validated Copper Cu Lead Pb Manganese Mn Mercury Hg Molybdenum Mo Nickel Ni Selenium Se Silver Ag Thallium Tl Thorium Th Uranium U Vanadium V Zinc Zn Calcium Ca Iron Fe Non-Trace Elements Magnesium Mg Potassium K Sodium Na

LOD 0.8 1.5 0.5 0.7 0.04 0.5 0.8 2.0 1.5 0.4 1.4 0.8 0.8 0.8 0.8 1.0 0.8 0.8 1.0 0.7 70 20 20 30 26

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Reagents, Solutions, and Standards All solutions prepared for use in this method must be stored in polyethylene containers the use of glassware is not acceptable. The useful lifetime of these solutions is no more than about one week. Analytical grade deionized water (DI H2O). Must have a resistivity of 17.518.5 M/cm. Concentrated nitric acid (HNO3). Trace metals analysis grade. Diluent solution. Must contain 1.0 % concentrated HNO3 by volume. Combine 100 mL trace metals analysis grade concentrated HNO3 in several liters of DI H2O, and bring to a total final volume of 10 L with DI H2O. Mix thoroughly. ICP-MS tuning solution. Contains 10 ppb Li, Y, Ce, Tl, and Co for instrument tuning and verification of performance. Mixed from single element standards of 1000 ppm concentration: Preparation of stock solution: Pipette 1 mL of each element solution into 100 mL volumetric flask and fill with 1% HNO3 diluent. Preparation of tuning solution: Pipette 1 mL of stock solution in 1000 mL flask and fill with 1% HNO3 diluent. Multi-element primary standard mixture. Contains Fe, K, Ca, Na, and Mg at 1000 ppm and Ag, Al, As, Ba, Be, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, Se, Tl, V, Zn, Th, and U at 10 ppm. Available from Agilent, item number 5183-4688. Single-element primary standards. If elements in addition to those contained in the multi-element primary standard are to be determined, working standard solutions may be supplemented with single-element standards to produce the desired concentrations. Single-element standards of suitable quality for plasma methods are available from a variety of sources. Internal standards (ISTD) primary standard mixture. Contains Li6, Sc, Ge, Y, In, Tb, and Bi at 10 ppm for use as internal standards. Available from Agilent, item number 5183-4680. Working ISTD solution. To prepare the working internal standards solution (1 ppm each IS), add 10 mL IS primary standard mixture to approximately 50 mL diluent solution and dilute to a total final volume of 100 mL with diluent solution. Erbium primary standard. Contains Er at 1 ppm for use as a dilution standard. Available from Agilent, item number G1820-60372. Working erbium solution. To prepare the working dilution standard solution (50 ppb Er), add 12.5 mL 1 ppm Er to approximately 100 mL diluent solution and dilute to a total final volume of 250 mL with diluent solution.

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Calibration standards. To prepare initial calibration (ICAL) solutions, specific volumes of the multi-element primary standard mixture are diluted with diluent solution. The required volumes of multi-element primary standard mixture for preparation of a standard set of ICAL solutions is given below (Table II), followed by the resultant concentration of all analytes at each calibration level (Table III). If additional elements are desired, single-element standards must be used to supplement the preparations described below. In order to obtain the concentrations listed in Table III, the total final volume of each solution must be 250.0 mL. If any of the elements are expected to exceed the calibration range given below, additional levels may be used in order to span the necessary range of concentrations using the multi-element or single-element standards as appropriate.
Table II. Preparation of ICAL standards. Volume, primary standard mixture (L) 0.0 5.0 10.0 50.0 100.0 500.0 1000.0

Level 1 2 3 4 5 6 7

Table III. Typical ICAL Levels. Analyte(s) Fe, K, Ca, Na, and Mg Ag, Al, As, Ba, Be, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, Se, Tl, V, Zn, Th, and U 1 Blank Blank Concentration (ppb) of Analyte at ICAL Level: 2 3 4 5 6 7 50 100 500.0 1,000.0 5,000.0 10,000 0.5 1.0 5 10.0 50.0 100.0

Sample Collection, Preparation, and Storage Samples must be collected and stored at all times in polyethylene containers. For the determination of dissolved elements in water, the sample must first be 0.45 m filtered, then preserved with 1.0% concentrated HNO3 by volume (0.5 % concentrated HCl is only added if Ag is of interest). For the determination of total recoverable elements in water, unfiltered samples are to be acidified with HNO3 as described above. In all cases, the pH of the samples should be verified to be less than 2.0 prior to analysis. The holding time for properly preserved aqueous samples is 6 months.

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Solid samples require no form of preservation. Any solid material to be processed for total recoverable elements should be stored at 4C at all times. No holding times have been established for solid samples. More detailed procedures for treatment of water samples as well as protocols for digestion of solid materials are available in EPA Method 200.8. Daily Procedures for Instrument Setup Prior to operating the ICP-MS, the following steps must be performed on a daily basis. These steps assume that the instrument hardware and software is configured for the 200.8 ICP-MS application. If the configuration is set for another application (i.e., LC-ICP-MS), see Appendix A for detailed instructions regarding setup of the hardware and software for the 200.8 ICP-MS application. 1. Replace all peristaltic pump tubing. When ready for analysis, clamp the tubing in place on the pumps. Place the lines for uptake of diluent and internal standard solutions into the appropriate vessels (refer to Appendix B for a detailed diagram of the tubing configuration). 2. Ensure that there is sufficient argon and helium supply. 3. Verify that the hydrogen generator is functioning properly. 4. Turn the chiller unit on prior to igniting the plasma. 5. Verify that all waste lines are in place, and empty waste reservoirs if needed. 6. Verify that ventilation is operating properly prior to igniting the plasma. 7. On the Agilent ICP-MS ChemStation software, enter the ICP-MS Top, and open the Instrument Control window. Click Plasma On. 8. Once the Plasma started check if Ar tank pressure and Ar carrier gas pressure have the right value. The values correspond to the used nebulizer and can be found in the Hardware Manual book. Adjust the pressure by opening or closing the regulation valve at the Ar-tank. 9. Once the plasma parameters have reached their setpoints, the instrument control window can be closed. Ensure that the 200.8 method (2008.M) is loaded (Method Load and run method). Next, enter the tune menu, and perform a sensitivity check of each of the three tune files utilized by the acquisition method (i.e., h2aset.U, heaset.U, and normaset.U). Once a tune file is loaded, use the ALS Go To command to send the autosampler probe to a vessel

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Analysis of Elements by EPA 200.8

containing tuning solution. Go to ISIS Prerun, allow time for the solution to reach the plasma, and start acquisition. Compare the responses to those in the ICP-MS reference notebook. 10. Perform a pulse to analog (P/A) factor tuning for each tune step as follows: Insert tubing into the ISTD solution. Go to tuning mode normal Go to Tune P/A Factor and Load Masses from Acquisition Method delete all elements except for: Na, Mg, Li, K, Sc, Y, Ge, In, Bi, Using the ALS Go To command, send the autosampler probe to ICAL level 2 (0.5 ppb) and start P/A factor, If sensitivity is too low for P/A factors use calibration solution 3 Go to Tune P/A Factor and Load Masses from Acquisition Method delete all elements except for: Be, Al, Mn, Co, Y, Tl, Th, U Using the ALS Go To command, send the autosampler probe to ICAL level 6 (50 ppb), check box for insert values and start P/A factor. Go to Tune P/A Factor and Load Masses from Acquisition Method delete all elements except for: Ni, Zn, As, Se, Mo, Ag, Cd, Sb, Ba, Pb, and all elements that had too low sensitivity with calibration solution 6. Using the ALS Go To command, send the autosampler probe to ICAL level 7 (100 ppb) check box for insert values and start P/A factor. Go to tuning mode H2 Go to Tune P/A Factor and Load Masses from Acquisition Method delete all elements except for: Ca, Fe, Ge, Y, Se, Sc Using the ALS Go To command, send the autosampler probe to ICAL level 3 and start P/A factor Go to Tune P/A Factor and Load Masses from Acquisition Method delete all elements except for: Cr, Cu Using the ALS Go To command, send the autosampler probe to ICAL level 7 and start P/A factor, check box for insert values Go to tuning mode He Go to Tune P/A Factor and Load Masses from Acquisition Method delete all elements except for: Ge, V, As, Se, Y Using the ALS Go To command, send the autosampler probe to ICAL level 7 and start P/A factor University of Alaska Anchorage (ASET)

Analysis of Elements by EPA 200.8

Usually only Be, Zn, As, Se and Ba have too low sensitivity all other elements should express a value <1. !Make sure you never measure Ca & Fe in normal mode it can destroy the detector! Analysis Sample analysis is carried out using an Agilent Technologies 7500c ICPMS equipped with the octopole reaction system. The reaction cell allows a nearvacuum interface between the plasma and the mass spectrometer, or may alternatively be flooded with a reaction or collision gas in order to minimize various interferences. In order to minimize known possible interferences, each element is acquired in one of three segments, or tune steps, of an analysis: no reaction gas (normal mode), He collision, or H2 reaction. Elements occurring at mass to charge ratios (m/z) with no anticipated plasma-based or matrix-based interferences are acquired in normal mode. In general, these include the relatively light and relatively heavy elements. Any element occurring at an m/z with a known matrix-based interference would be acquired in He collision mode. Polyatomic interferents occurring in the plasma as a result of matrix composition will be obstructed by the He gas to a greater degree than an analyte of the same mass owing to the smaller crosssectional area of the analyte compared to that of the polyatomic interferent. The result is reduced interference with a relatively small reduction in analyte signal, thereby enhancing the signal to noise ratio. Elements occurring at any m/z with a known argon-based interference are acquired in H2 reaction mode. Since the plasma is composed of argon, there is inherently a tremendous abundance of Ar+ ions present in the plasma. These may act as an interferent directly at m/z 40, or may participate in the formation of argon-containing polyatomic ions of the type ArM+. Flooding the reaction cell with H2 results in the following: 2 Ar+ + H2 2 Ar + 2 H+ Ar+ is reduced to neutral Ar and therefore does not enter the mass spectrometer or form polyatomic ions. It should be noted that H2 can act as a collision gas as well, and in fact the collisional obstruction of lighter elements by H2 is considerable. However, this is far less significant when considering heavier elements. In any case, H2 acts as a poorer collision gas than He due to H2s relatively small cross-sectional area compared to that of He.

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Table IV outlines the tune step in which each element is acquired, which isotope is acquired (if applicable), and internal standard element and isotope being utilized for that analyte. In addition, Tables V-IX outline the remaining acquisition parameters and instrument settings applied during this analysis.
Table IV. Tune step and internal standard m/z for each analyte m/z. Analyte / m/z IS / m/z Tune Step Be / 9 Li / 6 3 (Normal) Na / 23 Y / 89 3 (Normal) Mg / 24 Y / 89 3 (Normal) Al / 27 Y / 89 3 (Normal) K / 39 Y / 89 3 (Normal) Ca / 40 Sc / 45 1 (H2) V / 51 Sc / 45 2 (He) Cr / 52 Sc / 45 1 (H2) Mn / 55 Y / 89 3 (Normal) Fe / 56 Y / 89 1 (H2) Co / 59 Y / 89 3 (Normal) Ni / 60 Y / 89 3 (Normal) Cu / 63 Y / 89 1 (H2) Zn / 66 Y / 89 3 (Normal) As / 75 Y / 89 3 (Normal) Se / 77 Y / 89 3 (Normal) Se / 78 Y / 89 1 (H2) Mo / 98 Y / 89 3 (Normal) Ag / 107 In / 115 3 (Normal) Cd / 114 In / 115 3 (Normal) Sb / 121 In / 115 3 (Normal) Ba / 137 In / 115 3 (Normal) Tl / 205 Bi / 209 3 (Normal) Pb / 208 Bi / 209 3 (Normal) Th / 232 Bi / 209 3 (Normal) U / 238 Bi / 209 3 (Normal) Table V. Interference equations. Mass Equation 6 (6)*1 (7)*0.0813 115 (115)*1 (118)*0.0149 208 (208)*1 + (207)*1 + (206)*1 Table VI. Acquisition parameters. Acquisition mode Peak pattern Number of points per mass Integration time per point Number of repetitions Total acquisition time Detector Stabilization time, tune step 1 (tune file: mt_h2.u) Stabilization time, tune step 2 (tune file: mt_he.u) Stabilization time, tune step 3 (tune file: mt_norm.u)

Spectrum multi-tune Full quant 3 0.10 sec 3 168 sec Auto (P/A) 30 sec 30 sec 5 sec

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Analysis of Elements by EPA 200.8

Table VII. ISIS peristaltic pump program. Uptake speed Uptake time Before Acquisition Stabilization time (undiluted) Stabilization time (diluted) Rinse speed After Acquisition Rinse time (sample) (probe rinse) Rinse tine (standard) Rinse vial After Acquisition Uptake speed (rinse) Uptake time Stabilization speed Stabilization time

0.70 rps 20 sec 40 sec 70 sec 0.05 rps 5 sec 5 sec 1 0.70 60 sec 0.02 rps 0 sec

Table VIII. ISIS autodilution settings. 20 Dilution factor On (periodic mode) Correction 166 amu Std element Online IS element 159 amu Dilute all samples Off

Table IX. Plasma conditions. 1500 W RF power S/C Temperature 2C 1.00 L / min Carrier gas flow Makeup gas flow 0.42 L / min Peri pump speed 0.10 rps 8.4 mm Sample depth x.x mm Torch H x.x mm Torch V

Quality Control Internal standard performance. The response of each internal standard is monitored throughout all standard, analysis, and quality control samples. The initial response in counts per second (cps) for each IS is established when analyzing the calibration blank. All subsequent cps values for each IS must be within the range of 60% - 125% of the initial baseline value. If this condition is not satisfied, the elements quantitated using that IS may not be reported unless the sample is reanalyzed with satisfactory IS recovery. Continuing calibration verification (CCV). For every ten samples, a CCV is analyzed in order to verify the integrity of the instrument calibration. The CCV may be prepared by adding 1.25 mL of the multi-element primary standard mixture to approximately 100 mL diluent solution and dilute to a total final volume of 250 mL with diluent solution. This results in a concentration of 5000 ppb in Fe, K, Ca, Na, and Mg and a concentration of 50 ppb in Ag, Al, As, Ba, Be, Cd, Co,

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Analysis of Elements by EPA 200.8

Cr, Cu, Mn, Mo, Ni, Pb, Sb, Se, Tl, V, Zn, Th, and U. The analytical result for concentration of each element in the CCV must be within 85% - 115% of the actual value. If this condition is not satisfied, the failing element(s) may not be reported in the affected samples. If reanalysis of the CCV does not produce satisfactory results, recalibration may be necessary. Once satisfactory performance of the CCV is achieved, any affected samples may be reanalyzed. Overall performance verification. An international standard for trace metals in water (NIST 1643) is measured undiluted to verify the overall performance of the trace metal analysis. This performance is tested once a month. The recovery of the standard must be between 85% to 115% for environmental analysis.
Table x: True and measured values for the NIST standard 1643
Element Ag Al As Ba Be Cd Co Cr Cu Fe K Mn Mo Ni Pb Sb Se Th Tl U V Zn Ca Mg Na concentration g/kg 7.6 52.0 26.7 148.0 34.9 22.8 20.3 38.6 85.2 34.3 994.0 121.5 46.8 27.4 27.9 13.8 22.0 Nd Nd Nd 13.0 53.2 mg/kg 7.0 5.8 29.4 Measured n=4 g/kg 8.4 51.8 26.0 145.2 34.0 22.5 20.5 34.3 84.3 42.3 1035.1 123.7 46.8 27.8 27.7 14.4 18.8 Dev % 11 0 -3 -2 -3 -1 1 -11 -1 23 4 2 0 1 -1 5 -14

13.5 52.1 mg/kg 6.8 5.9 30.3

4 -2 3 2 3

Continuing calibration blank (CCB). For every ten samples, a CCB consisting of unsupplemented diluent solution is analyzed in order to determine the presence or absence of unacceptable carryover. If the analytical result obtained for a CCB is greater than 0.5 ppb for trace elements or 50 ppb for nontrace elements, the affected elements may not be quantitated. Reanalysis of the

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Analysis of Elements by EPA 200.8 10

CCB should be performed after rinsing the system with DI H2O. Samples may be reanalyzed after acceptable blank levels have been attained. Calibration range exceeded. If any element in a sample is found to exceed the range of calibration, the sample is to be diluted into the appropriate range and reanalyzed. This may be accomplished by automated means using the Agilent 7500c ICP-MS integrated sample introduction system (ISIS). When a sample result is greater than a used defined maximum (i.e., the concentration of the highest ICAL level), the sample is subjected to online ISIS dilution by a factor of twenty and reanalyzed. The original concentration is the calculated and reported using an exact dilution factor established by analyzing a 50 ppb erbium solution at undiluted and diluted levels. The exact dilution factor (DF) is given by:

DF =

(ErU )(Tb D ) (ErD )(Tb U )

Where ErU is the undiluted cps of erbium (m/z 166), TbD is the diluted cps of the internal standard terbium (m/z 159), ErD is the diluted cps of erbium, and TbU is the undiluted cps of terbium. If autodilution fails to bring the analyte concentrations into the appropriate range, the result is reported as being greater than the limit of calibration. In order to obtain a result, manual dilution according to the judgment of the analyst may be required. References EPA Method 200.8, Revision 5.4, U.S. Environmental Protection Agency, Cincinnati, OH, 1994.

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Analysis of Elements by EPA 200.8 11

Appendix A Changing the Hardware and Software Configuration to ICP-MS from LC-ICP-MS The ICP-MS system may also be utilized in tandem with LC to perform metals speciation analyses such as arsenic speciation (see ASET arsenic speciation protocol). When the instrument is being routinely utilized in different applications, the analyst will be required to modify certain hardware and software configurations in order to change from one application to the next. This appendix summarizes the changeover procedures to ICP-MS from LC-ICP-MS. To change from LC-ICP-MS to ICP-MS:
Hardware

Plug the serial cable from the ISIS communications box into the remote port on the lower left corner of the ICP-MS rear panel. Turn the ISIS box on. Carefully remove the concentric nebulizer and attached tubing from the spray chamber interface, and replace with the standard Babbington nebulizer and associated plumbing (see Appendix B for the full tubing configuration). Be especially sure that the nebulizer is fully seated and well sealed and that the makeup gas and carrier gas lines are properly attached.
Software

Enter the configuration panel. Under Remote Start, select Dont Use. Under Sample Introduction, set the type to ISIS, and set the ISIS Application to Autodilution. On the Autosampler menu, select the ASX500. Next to the autosampler drop-down menu, click Setup. The ID for Racks 1, 2, 3, and 4 should be set for 21, 60, 60, and 60, respectively. Click OK. Next, click on Miscellaneous, and change the Remote Shutdown to Standard. Once these changes are complete, click Save (if you do not click Save, your changes will not be made!).

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Analysis of Elements by EPA 200.8 12

Appendix B

Tubing and Hardware Configuration for Autodilution with ISIS Provided by Emmett Soffey, Agilent Technologies

Tubing and Hardware Configuration for Autodilution with ISIS

1
1 mm 2stop tygon. Trim ~ 1 inch from stops. 1mm 2 stop tygon.

ISIS #1 4 3

ISIS #2

ASX-500

5
The teflon tubing incorporated into the flow paths from both the ASX-500 and Diluent should be 0.5 mm up to this point. At some sites customers have installed 0.8mm tubing between item 6 and 13 in order to minimize backpressure during rapid uptake.

6 12

13
The teflon tubing downstream of this point may be 0.3 or 0.5 mm tubing. See explanation below. 1.0 or 0.89 mm 3 stop tygon. Trim this tubing so that only two stops remain with tubing extending ~3/4 inch beyond stops.

2mm Teflon drain tube

Diluent
0.25mm 3 stop tygon tubing

Large Waste Container

Items 7 and 8 refer to peri pump tubing on channels 1&2 of the 7500 peri pump or channel 1&2 of peri pump #1 on the 4500.

Nebulizer
Denotes sections of teflon tubing that should be as short as possible.

10
1mm 2 Stop Tygon (See note for Item 1&2)

11 ISTD

1.0 or 0.89mm 3 Stop Tygon (See note for Item 7) 0.19 or 0.25mm 3 Stop Tygon(See note for Item 8) 0.5mm ID Teflon 0.3 or 0.5 mm ID Teflon 2mm ID Teflon for Drain

**The peri pump tubing connected to the spray chamber drain has been omitted from this diagram.

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