Multi-Elemental Analysis of Aqueous Geochemical Samples 

by Quadrupole Inductively Coupled Plasma-Mass 

Spectrometry (ICP-MS) 

By Ruth E. Wolf and Monique Adams

Open-File Report 2015–1010

U.S. Department of the Interior

U.S. Geological Survey
ii

U.S. Department of the Interior

SALLY JEWELL, Secretary

U.S. Geological Survey

Suzette M. Kimball, Acting Director

U.S. Geological Survey, Reston, Virginia: 2015

For more information on the USGS—the Federal source for science about the Earth,

its natural and living resources, natural hazards, and the environment—visit

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For an overview of USGS information products, including maps, imagery, and publications,

visit http://www.usgs.gov/pubprod/.

Any use of trade, firm, or product names is for descriptive purposes only and does not imply

endorsement by the U.S. Government.

Although this information product, for the most part, is in the public domain, it also may

contain copyrighted materials as noted in the text. Permission to reproduce copyrighted items

must be secured from the copyright owner.

Suggested citation:

Wolf, R.E., and Adams, Monique, 2015, Multi-elemental analysis of aqueous geochemical samples by quadrupole 

inductively coupled plasma-mass spectrometry (ICP-MS): U.S. Geological Survey Open-File Report 2015–1010, 

p. 34, http://dx.doi.org/10.3133/ofr20151010.

ISSN 2331-1258 (online)
iii

Contents

Principle......................................................................................................................................................................... 1

Interferences and Other Sources of Analytical Bias....................................................................................................... 1

Scope ............................................................................................................................................................................ 3

Apparatus ...................................................................................................................................................................... 3

Reagents ....................................................................................................................................................................... 7

Internal Standards ......................................................................................................................................................... 7

Calibration Standards .................................................................................................................................................... 7

Safety Precautions........................................................................................................................................................11

Sample Preparation......................................................................................................................................................11

Procedure.....................................................................................................................................................................11

Method Performance—Blank Analysis and Reporting Limits........................................................................................13

Method Performance—Analyses of Quality Control Samples.......................................................................................16

References Cited..........................................................................................................................................................29

Appendix 1. Determination of Empirical Oxide Corrections ..........................................................................................31

Tables

1. Elements determined in aqueous samples by Inductively Coupled Plasma-Mass Spectrometry and

determination parameters .................................................................................................................................... 4

2. Attenuation levels achieved using Extended Dynamic Range mode ................................................................... 7

3. Sources, elements, and concentrations of commercially available stock solutions.............................................. 8

4. Elements and concentrations of Water Matrix Stock solution .............................................................................. 9

5. Preparation and final concentration of calibration standards for Inductively Coupled Plasma-Mass 

Spectrometry (ICP-MS) analysis........................................................................................................................ 10

6. ELAN DRC-e operating parameters................................................................................................................... 12

7. Preparation and final concentration of independent calibration verification standards for Inductively 

Coupled Plasma-Mass Spectrometry (ICP-MS) analysis................................................................................... 12

8. Blanks analysis, method detection limits, and reporting limits............................................................................ 14

9. Analysis of quality control samples .................................................................................................................... 16

1–1. Elements and timing parameters for oxide interference correction determination.............................................. 31 

1–2. Correction equations calculation worksheet with formulas used for calculations shown.................................... 34
iv

Conversion Factors

Inch/Pound to SI

Multiply By To obtain

Length

inch (in.) 2.54 centimeter (cm)

inch (in.) 25.4 millimeter (mm)

Volume

ounce, fluid (fl. oz) 0.02957 liter (L) 

pint (pt) 0.4732 liter (L) 

quart (qt) 0.9464 liter (L) 

gallon (gal) 3.785 liter (L) 

gallon (gal) 0.003785 cubic meter (m3) 

cubic inch (in3) 16.39 cubic centimeter (cm3) 

cubic inch (in3) 0.01639 liter (L)

Flow rate

foot per second (ft/s) 0.3048 meter per second (m/s)

foot per minute (ft/min) 0.3048 meter per minute (m/min)

Mass

ounce, avoirdupois (oz) 28.35 gram (g) 

pound, avoirdupois (lb) 0.4536 kilogram (kg) 

Pressure

atmosphere, standard (atm) 101.3 kilopascal (kPa)

bar 100 kilopascal (kPa) 

Density

pound per cubic foot (lb/ft3) 0.01602 gram per cubic centimeter 

(g/cm3)

Energy

kilowatthour (kWh) 3,600,000 joule (J)

Specific conductance is given in microsiemens per centimeter at 25 degrees Celsius (μS/cm at 25 °C).

Concentrations of chemical constituents in water are given either in milligrams per liter (mg/L) or micrograms per liter (μg/L).
1

Multi-Elemental Analysis of Aqueous Geochemical 

Samples by Quadrupole Inductively Coupled Plasma-Mass 

Spectrometry (ICP-MS) 

By Ruth E. Wolf and Monique Adams

Principle

Typically, quadrupole inductively coupled plasma-mass spectrometry (ICP-MS) is used to 

determine as many as 57 major, minor, and trace elements in aqueous geochemical samples, including 

natural surface water and groundwater, acid mine drainage water, and extracts or leachates from

geological samples. The sample solution is aspirated into the inductively coupled plasma (ICP) which 

is an electrodeless discharge of ionized argon gas at a temperature of approximately 6,000 degrees 

Celsius. The elements in the sample solution are subsequently volatilized, atomized, and ionized by the 

ICP. The ions generated are then focused and introduced into a quadrupole mass filter which only 

allows one mass to reach the detector at a given moment in time. As the settings of the mass analyzer 

change, subsequent masses are allowed to impact the detector. Although the typical quadrupole ICP-MS 

system is a sequential scanning instrument (determining each mass separately), the scan speed of 

modern instruments is on the order of several thousand masses per second. Consequently, typical total 

sample analysis times of 2–3 minutes are readily achievable for up to 57 elements. 

For the protocol described, the ICP-MS is calibrated using a blank and a minimum of four 

standards prepared from commercially available multi-element standard solutions in conjunction with 

two standards for phosphorus and sulfur. At the discretion of the analyst, additional elements may be 

determined after suitable method modifications and performance data are established. Calibration curves 

are verified using a minimum of one standard prepared from a second commercial source and two 

reference water samples or certified reference materials obtained from a commercial source in a ready to 

analyze state. Samples to be analyzed for “dissolved” constituents must be filtered and acid-preserved in 

1–2 percent nitric acid (HNO3) at sample collection or as soon as possible after collection prior to 

analyses (no digestion is required). Samples to be analyzed for “total” elements require a digestion 

before analysis such as U.S. Environmental Protection Agency (EPA) Method 3015A—Microwave 

Assisted Acid Digestion for Aqueous Samples and Extracts (U.S. Environmental Protection Agency, 

2007a). This method may also be used to analyze digested biological samples including insects, plants, 

and biological tissue. 

Interferences and Other Sources of Analytical Bias

ICP-MS interferences come from spectroscopic and nonspectroscopic (or matrix) sources 

(Jarvis, 1992). Spectroscopic interferences include direct isobaric overlaps, where an isotope of one 

element exists at the same nominal mass as an isotope of another element, for example chromium and 

iron both have naturally occurring isotopes at mass 54 (54Cr and 54Fe). Polyatomic isobaric 

interferences may occur because of the formation of ions from plasma and sample matrix species; for 

example, 40Ar from the plasma and 35Cl from samples containing chloride or hydrochloric acid form 

40Ar35Cl+ at mass 75, interfering with the determination of arsenic at 75As+

. Double-charged 
2

interferences can occur when an element forms a double-charged species in the plasma and can interfere 

with elements at lower masses; for example, in high barium matrices, 138Ba2+ formation in the plasma 

results in a signal at a mass-to-charge ratio of 69, interfering with the determination of gallium at 69Ga. 

Refractory oxides can result from incomplete atomization of the sample matrix or recombination of the 

species in the plasma. Plasma tuning parameters such as radio frequency (RF) power and cooling, 

auxiliary, and sample argon flows are generally established during the instrument tuning process to 

minimize oxide formation; however, for some applications, such as the determination of rare earth 

elements (REEs), oxide formation is a serious source of interference and analytical bias. Commonly, the 

isotopes measured for each element to be determined are selected to minimize isobaric overlap from

other elements and molecular species that may be present in the sample matrix or formed in the argon 

plasma. For some isotopes, isobaric overlap corrections are computed based on relative isotopic 

abundances of the elements involved, and oxide or double-charged ion intensities. For the REEs, 

empirical oxide correction equations are used that must be re-evaluated on a routine basis when 

instrument tuning parameters are changed. Instrumentation with Dynamic Reaction Cell (DRC) 

technology (Perkin Elmer, Inc., Shelton, Conn.) also has the capability to use different reaction gases in 

the DRC cell between the ICP ion source and the analyzer quadrupole to break apart and remove 

molecular interferences or to shift the analyte ion away from a nonremovable interference by selective 

gas phase reaction chemistry (Tanner and others, 2002). 

Nonspectroscopic interferences include effects that cause suppression or enhancement of the 

analytical signal or physical effects caused by high total dissolved solids. Nonspectroscopic effects are 

commonly referred to as matrix effects, because they can vary with each sample matrix type. Matrix 

effects are often unpredictable and not well understood. Known matrix effects include viscosity 

differences between different types and (or) concentrations of acids that result in changes in sample 

uptake, nebulization, and vaporization rates (Olesik and Bates, 1995). Specific examples include signal 

enhancements observed in matrices containing organic solvents, signal suppression of low mass 

elements in solutions containing significant levels of high mass elements, signal enhancements of 

certain elements in high carbon-containing solutions, and suppression of some elements in the presence 

of easily ionizable elements such as Na, K, and Cs (Allain and others, 1991; Jarvis, 1992; Kralj and 

Veber, 2003). High levels of total dissolved solids can lead to partial clogging of the sample interface 

cones between the atmospheric ICP discharge and the high vacuum of the mass analyzer and result in 

significant levels of signal drift over time. Although matrix interferences can be minimized by careful 

matching of sample and calibration matrices, the use of internal standards is generally required to 

compensate for matrix effects and long-term instrumental drift (Lichte and others, 1987; Jarvis, 1992; 

Horlick and Montaser, 1998). When internal standards are used, the ratio of the analyte intensity to the 

internal standard intensity is calculated and used in all subsequent calibration calculations. 

Most aqueous samples are not digested prior to analysis, but usually they will have been filtered. 

Samples that have been filtered and acid preserved (FA) generally do not require additional filtering 

unless particulate matter has precipitated during storage and transport. Raw, acidified (RA) samples that 

have not been filtered at collection may contain particulate material because some elements will 

precipitate over time. At the analyst’s discretion, these samples may be filtered (using 0.45 μm 

disposable syringe filters) or decanted prior to analysis to prevent particulate matter from clogging the 

sample introduction system (for example, the sample probe or nebulizer). Samples with conductivities 

greater than 1,500 μS/cm or total dissolved solids (TDS) levels of greater than 0.1 percent are generally 

diluted by the analyst in order to prevent clogging of the sample introduction system and minimize 

matrix interferences. The analyst should notify the sample submitter if this or any other procedures were 

necessary to analyze the samples.
3

Scope

ICP-MS has been applied to the determination of 57 elements in various aqueous matrices, 

including natural waters, acid mine drainage waters, and extract and leachate samples. Analytes for 

which EPA has demonstrated the acceptability of ICP-MS determinations for waters and waste extracts 

(U.S. Environmental Protection Agency, 2007b) are included in this work. In addition to the 23 EPA 

target analyte list (TAL) elements, 34 elements are included in this protocol per the provisions of 

Method 6020A, including the REEs. The elements analyzed, masses utilized, and interference correction 

equations utilized are shown in table 1. 

Some major elements are determined using extended dynamic range (EDR) mode in order to 

limit the need to dilute samples. In EDR mode, the quadrupole inside the DRC is utilized in direct 

current (dc) voltage-only mode without a reaction cell gas to attenuate the ion beam passed through to 

the analyzer quadrupole (Tanner and Baranov, 1999; Abou-Shakar, F., 2005), resulting in higher linear 

ranges. In order to implement EDR mode, the elements expected to be at high concentrations in the 

samples are analyzed with the DRC parameter RPa at two or three nonzero values in addition to the 

normal mode value of RPa=0 while the RF-controlling parameter, RPq, is held at the normal mode 

value of RPq=0.25. The values of RPq and RPa control the mass bandpass in the DRC. RPq is the low 

mass cutoff and controls the RF applied to the quadrupole rods in the DRC. RPa is analogous to a high 

mass cutoff and controls the dc voltage applied to the quadrupole rods in the DRC (Tanner and others, 

2002). The elements in EDR mode can be determined at various RPa attenuation values within the same 

analytical run, eliminating the need to dilute most samples. Table 2 shows some examples of the levels 

of signal attenuation that can be obtained using the EDR mode. 

Apparatus

• Quadrupole Inductively Coupled Plasma-Mass Spectrometer equipped with Dynamic Reaction 

Cell (PerkinElmer ELAN DRC-e, ELAN DRCII, NexION 300D, or NexION 350D are the 

models currently used, PerkinElmer Life and Analytical Sciences, Shelton, Conn.) 

• Random access autosampler compatible with ICP-MS instrumentation listed above 

• Peltier-cooled quartz spray chamber (Model PC–3, Elemental Scientific, Inc., Omaha, Nebr.) or 

quartz cyclonic spray chamber (PerkinElmer Life and Analytical Sciences, Shelton, Conn.) 

• Glass or quartz concentric nebulizer, 0.5–1.0 milliliter per minute (mL/min) uptake rate, A- or 

C-type (Meinhard Inc., Golden, Colo.) 

• 13 x 100 millimeter (mm) disposable, polypropylene test tubes with caps (VWR International, 

Radnor, Pa., vials part number 60818–860 and caps part number 60828–738) 

• Adjustable mechanical or electronic pipettes, typical volume ranges needed are from 5 to 120 

microliters (μL), from 50 to 1,000 μL, and from 100 to 5,000 μL 

• 15 and 50 milliliter (mL) BD Falcon polypropylene tubes (BD Biosciences, San Jose, Calif.) 

• Peristaltic pump tubing, polyvinyl chloride (PVC) type (Meinhard Inc., Golden, Colo.): 

o Internal standard: Orange-orange (0.89 mm inner diameter [i.d.]) 

o Sample: Orange-orange (0.89 mm i.d.) 

o Drain: Purple-purple (2.06 mm i.d.) 

• Autosampler peristaltic pump tubing, Santoprene type: Red-red (1.14 mm i.d.), 3-stop 

• Plastic mixing tee (1/16-in. i.d.) (Cole-Parmer, EW–30506–15) 
4

Table 1. Elements determined in aqueous samples by Inductively Coupled Plasma-Mass Spectrometry and determination parameters. 

[cps, counts per second; MCA, multichannel analyzer; ms, milliseconds; EDR, extended dynamic range; IEC, interelement correction] 

Internal 

standard Analyte Mass Scan mode MCA channels Dwell time Integration time Mode Equations Equationtype

Li 6.015 Peak Hopping 1 50.0 ms 750 ms Normal

6 Li Li 7.016 Peak Hopping 1 50.0 ms 750 ms Normal

6 Li Be 9.012 Peak Hopping 1 50.0 ms 750 ms Normal

103 Rh Na 22.99 Peak Hopping 1 50.0 ms 750 ms Normal

103 Rh Na-1 22.99 Peak Hopping 1 50.0 ms 750 ms EDR -

Rpa=0.014

103 Rh Na-2 22.99 Peak Hopping 1 50.0 ms 750 ms EDR -

Rpa=0.016

103 Rh Mg 24.986 Peak Hopping 1 50.0 ms 750 ms Normal

103 Rh Al 26.982 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Al-1 26.982 Peak Hopping 1 50.0 ms 750 ms EDR -

Rpa=0.012

103 Rh Si 28.977 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh P 30.994 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh S 33.968 Peak Hopping 1 50.0 ms 750 ms Normal

103 Rh K 38.964 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Ca 42.959 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Ca 43.956 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Sc 44.956 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Ti 48.948 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh V 50.944 Peak Hopping 1 20.0 ms 300 ms Normal –3.127*(ClO53–(0.113*Cr52)) Isobaric

103 Rh Cr 51.941 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Cr 52.941 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Fe 53.94 Peak Hopping 1 20.0 ms 300 ms Normal –0.028226 * Cr 52 Isobaric

103 Rh Mn 54.938 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Fe 56.935 Peak Hopping 1 20.0 ms 300 ms Normal –0.049304*Ca43 Empirical-IEC
5

Table 1. Elements determined in aqueous samples by Inductively Coupled Plasma-Mass Spectrometry and determination parameters.—Continued

[cps, counts per second; MCA, multichannel analyzer; ms, milliseconds; EDR, extended dynamic range; IEC, interelement correction] 

Internal 

standard Analyte Mass Scan mode MCA channels Dwell time Integration time Mode Equations Equationtype

103 Rh Ni 57.935 Peak Hopping 1 20.0 ms 300 ms Normal –0.0428*Fe54-0.0037*Ca43 Empirical-IEC

103 Rh Co 58.933 Peak Hopping 1 20.0 ms 300 ms Normal –0.001231*Ca43 Empirical-IEC

103 Rh Ni 59.933 Peak Hopping 1 50.0 ms 750 ms Normal –0.0025*Ca43 Empirical-IEC

103 Rh Cu 64.928 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Zn 65.926 Peak Hopping 1 20.0 ms 300 ms Normal –0.0026*Ti49 Isobaric

103 Rh Ga 70.925 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Ge 73.922 Peak Hopping 1 20.0 ms 300 ms Normal –0.116645 * Se 77 Isobaric

103 Rh As 74.922 Peak Hopping 1 100.0 ms 1500 ms Normal

103 Rh As-1 74.922 Peak Hopping 1 100.0 ms 1500 ms Normal –3.127*(ArCl77–0.825*Se82) Isobaric

103 Rh Se 76.92 Peak Hopping 1 100.0 ms 1500 ms Normal

103 Rh Se 81.917 Peak Hopping 1 100.0 ms 1500 ms Normal –1.007833 * Kr 83 Isobaric

103 Rh Rb 84.912 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Sr 87.906 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Y 88.905 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Zr 89.904 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Nb 92.906 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Mo 97.906 Peak Hopping 1 20.0 ms 300 ms Normal –0.110588 * Ru 101 Isobaric

Rh 102.905 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Ag 108.905 Peak Hopping 1 20.0 ms 300 ms Normal –0.006819*Nb93 Isobaric

103 Rh Cd 113.904 Peak Hopping 1 20.0 ms 300 ms Normal –0.027250 * Sn 118 Isobaric

103 Rh Sb 120.904 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Cs 132.905 Peak Hopping 1 20.0 ms 300 ms Normal

103 Rh Ba 134.906 Peak Hopping 1 20.0 ms 300 ms Normal

193 Ir La 138.906 Peak Hopping 1 20.0 ms 300 ms Normal
6

Table 1. Elements determined in aqueous samples by Inductively Coupled Plasma-Mass Spectrometry and determination parameters.—Continued

[cps, counts per second; MCA, multichannel analyzer; ms, milliseconds; EDR, extended dynamic range; IEC, interelement correction] 

Internal 

standard Analyte Mass Scan mode MCA channels Dwell time Integration time Mode Equations Equationtype

193 Ir Ce 139.905 Peak Hopping 1 20.0 ms 300 ms Normal

193 Ir Pr 140.907 Peak Hopping 1 10.0 ms 150 ms Normal

193 Ir Nd 145.913 Peak Hopping 1 10.0 ms 150 ms Normal –0.00034*Ba135 Empirical-IEC

193 Ir Sm 148.917 Peak Hopping 1 10.0 ms 150 ms Normal

193 Ir Eu 150.92 Peak Hopping 1 10.0 ms 150 ms Normal –0.001238*Ba135 Empirical-IEC

193 Ir Tb 158.925 Peak Hopping 1 10.0 ms 150 ms Normal –0.011207*Nd146 Empirical-IEC

193 Ir Gd 159.927 Peak Hopping 1 10.0 ms 150 ms Normal –0.079197*Dy164-0.0197*Nd146-

0.000596*Sm149 Empirical-IEC

193 Ir Dy 163.929 Peak Hopping 1 10.0 ms 150 ms Normal –0.046589*Er166-0.00542*Nd146-

0.00359*Sm149 Empirical-IEC

193 Ir Ho 164.93 Peak Hopping 1 10.0 ms 150 ms Normal –0.004782*Sm149 Empirical-IEC

193 Ir Er 165.93 Peak Hopping 1 10.0 ms 150 ms Normal –0.005547*Nd146 –0.002507*Sm 

149 Empirical-IEC

193 Ir Tm 168.934 Peak Hopping 1 10.0 ms 150 ms Normal –0.000804*Eu151 Empirical-IEC

193 Ir Yb 171.937 Peak Hopping 1 10.0 ms 150 ms Normal –0.008746*Gd160 Empirical-IEC

193 Ir Lu 174.941 Peak Hopping 1 10.0 ms 150 ms Normal

193 Ir Ta 180.948 Peak Hopping 1 20.0 ms 300 ms Normal –0.005965*Ho165 Empirical-IEC

193 Ir W 183.951 Peak Hopping 1 20.0 ms 300 ms Normal –0.004947*Er166 Empirical-IEC

Ir 192.963 Peak Hopping 1 20.0 ms 300 ms Normal

193 Ir Tl 204.975 Peak Hopping 1 50.0 ms 750 ms Normal

193 Ir Pb 207.977 Peak Hopping 1 20.0 ms 300 ms Normal +1*Pb206+1*Pb207 Isobaric

193 Ir Bi 208.98 Peak Hopping 1 20.0 ms 300 ms Normal

193 Ir Th 232.038 Peak Hopping 1 20.0 ms 300 ms Normal

193 Ir U 238.05 Peak Hopping 1 20.0 ms 300 ms Normal
7

Table 2. Attenuation levels achieved using Extended Dynamic Range mode. 

[cps, counts per second; mg/L, milligrams per liter; μg/L, micrograms per liter; %, percent] 

Rpa Na cps (5 mg/L standard) Attenuation factor

0.000 35153179 0

0.014 4127026 88.3%

0.016 128618 99.6%

Rpa Al cps (50 μg/L standard) Attenuation factor

0.000 330886 0

0.012 178419 46.1%

Reagents

• Deionized (DI) water, ASTM Type I, 18 megaohm (MΩ) (Milli-Q, EMD Millipore, Billerica, 

Mass.)

• Nitric acid (HNO3), concentrated (70 percent), sub-boiling distilled (Reagent grade HNO3, VWR 

International, Radnor, Pa., purified using Milestone DuoPur, Milestone, Shelton, Conn.) or 

ULTREX grade or equivalent

• Two percent HNO3 (vol/vol)—Dilute 40 mL concentrated HNO3 to 2,000 mL with DI water 

Internal Standards

Prepare 2 L of a solution containing 500 μg/L 6Li, 20 μg/L Rh, and 20 μg/L Ir by serial dilution 

of commercial 1,000 mg/L aqueous standards (High Purity Standards, Charleston, S.C.), using 2 percent 

HNO3. This solution is mixed in a 1:1 ratio with the sample to be analyzed using two channels of the 

instrument peristaltic pump equipped with a plastic mixing tee and two lines of the orange-orange (0.89 

mm i.d.) tubing. The concentrations of the internal standard solution may be adjusted, if necessary, to 

give target signal intensities between 200,000 and 600,000 counts per second (cps) for each internal 

standard element.

Calibration Standards

All calibration standards, continuous calibration verification (CCV) standards, and independent 

calibration verification (ICV) standards are prepared by serial dilution of commercially available multielement ICP-MS stock solutions and custom blended matrix stock solutions. The sources, elements, and 

concentrations of the commercially available stock solutions are given in table 3. The elements and 

concentrations of the Water Matrix Stock solution are given in table 4. The water matrix stock can either 

be prepared from single element ICP-grade 10,000 mg/L or 1,000 mg/L commercially available 

standards or custom ordered prepared at the concentrations listed in table 4. Two separate sources of the

Water Matrix Stock solution are required, one for preparation of the calibration standards and the 

second for the preparation of the independent calibration verification solution(s). Currently used sources 

of these custom-prepared standards include High Purity Standards (Charleston, S.C.) and Inorganic 

Ventures, Inc., (Christiansburg, Va.). The water matrix stock solution is added to the trace element stock 

solutions to provide an increasing concentration of common water matrix elements, reducing possible 

matrix effects from easily ionizable elements on trace element signal intensities (Horlick and Montaser, 

1998; Wolf and others, 2001). Other 1,000 mg/L stock standards used for calibration standard 

preparation are available commercially (High Purity Standards, Charleston, S.C.). The preparation of 
8

Table 3. Sources, elements, and concentrations of commercially available stock solutions. 

[mg/L, milligram per liter]

Name

Source

Part number

Concentration 

Calibration stock A

High Purity

ICP-MS-68A

10 mg/L

Calibration stock B

High Purity

ICP-MS-68B

10 mg/L

ICV stock 1A Inorganic

Ventures

IV-ICPMS-71A

10 mg/L

ICV stock 1B

Inorganic Ventures

IV-ICPMS-71B

10 mg/L

ICV stock 2A

PerkinElmer

N9300233

10 mg/L

ICV stock 2B

PerkinElmer

N9300232

10 mg/L

ICV stock 2C

PerkinElmer

N9300235

10 mg/L

Elements Al Ag Ag Ge Ag Ce B 

As Ge Al Hf Al Dy Ge

B Hf As Mo As Er Mo

Ba Mo B Nb Ba Eu Nb

Be Nb Ba Sb Be Gd P 

Bi Sb Be Si Bi Ho Re

Ca Si Ca Sn Ca La S 

Cd Sn Cd Ta Cd Lu Si

Ce Ta Ce Te Co Nd Ta

Co Te Co Ti Cr Pr Ti

Cr Ti Cr W Cs Sc W 

Cs W Cs Zr Cu Sm Zr

Cu Zr Cu Fe Tb

Dy Dy Ga Th

Er Er In Tm

Eu Eu K Y 

Fe Fe Li Yb

Ga Ga Mg

Gd Gd Mn

Ho Ho Na

In K Ni

K La Pb

La Lu Rb

Li Mg Se

Lu Mn Sr

Mg Na Tl

Mn Nd U 

Na Ni V

Nd P Zn

Ni Pb

P Pr

Pb Rb

Pr S

Rb Se

Re Sm

Sc Sr

Se Th

Sm Tl

Sr Tm

Tb U 

Th V 

Tl Yb

Tm Zn

U 

V 

Y 

Yb

Zn
9

the calibration standards and final concentrations are given in table 5. Note that because of the high 

sodium matrix in the commercially available phosphate and sulfate 1,000 mg/L stock standards, 25 

mg/L of Ca is added to the final prepared phosphate and sulfate calibration standards to eliminate signal 

enhancement effects caused by Easily Ionizable Element (EIE) effects. Standards are generally prepared 

to final volume by weight using the following procedure: (1) tare an empty 50 mL centrifuge tube on 

the balance; (2) pipette the designated amount of all stock solutions into the centrifuge tube; (3) add 2 

percent HNO3 (vol/vol) up to the final desired weight using a wash bottle containing 2 percent HNO3

prepared with sub-boiling distilled HNO3 [Note: for 2 percent (vol/vol) HNO3, the density is 1.0 g per 

1.0 mL. If higher acid concentrations are used, density corrections may be necessary to prepare final 

volumes by weight. The density of the acid concentration being used can be measured by determining 

the weight of 1.00 mL of the acid pipetted into a tared vessel]. 

Table 4. Elements and concentrations of Water Matrix Stock solution. 

[mg/L, milligram per liter]

Element Concentration

(mg/L)

Na 250

Ca 250

Mg 50

K 50

Si 50
10

Table 5. Preparation and final concentration of calibration standards for Inductively Coupled Plasma-Mass 

Spectrometry (ICP-MS) analysis. 

[cal., calibration; μg/L, microgram per liter; mg/L, milligram per liter; %, percent; mL, milliliter; μL, microliter; g, gram; 

mg, milligram] 

Cal. Standard 1 Stock solution Volume (μL) Final concentration (μg/L)

Cal. Standard 2 5 mL 1 μg/L (all elements)

2% HNO3 to 50 mL (or 50 g)

Cal. Standard 2 Stock solution Volume (μL) Final concentration (μg/L)

ICP-MS-68A (High Purity) 50 μL 10 μg/L (all elements)

ICP-MS-68B (High Purity) 50 μL 10 μg/L (all elements)

2% HNO3 to 50 mL (or 50 g)

Cal. Standard 3 Stock solution Volume (μL) Final concentration (μg/L)

ICP-MS-68A (High Purity) 250 μL 50 μg/L (all elements)

ICP-MS-68B (High Purity) 250 μL 50 μg/L (all elements)

Water Matrix Stock 1000 μL 5 mg/L Na, Ca; 1 mg/L Mg, K, Si

2% HNO3 to 50 mL (or 50 g)

Cal. Standard 4 Stock solution Volume (μL) Final concentration (μg/L)

ICP-MS-68A (High Purity) 500 μL 100 μg/L (all elements)

ICP-MS-68B (High Purity) 500 μL 100 μg/L (all elements)

Water Matrix Stock 5 mL 25 mg/L Na, Ca; 5 mg/L Mg, K, Si

2% HNO3 to 50 mL (or 50 g)

Cal. Standard 5 Stock solution Volume (μL) Final concentration (μg/L)

ICP-MS-68A (High Purity) 500 μL 250 μg/L (all elements)

ICP-MS-68B (High Purity) 500 μL 250 μg/L (all elements)

Water Matrix Stock 4 mL 50 mg/L Na, Ca; 10 mg/L Mg, K, Si

2% HNO3 to 20 mL (or 20 g)

Cal. Standard 6 Stock solution Volume (μL) Final concentration (μg/L)

(SO4 and PO4 Low) 1,000 mg/L PO4 2.5 mL 125 mg/L PO4/40.8 mg/L P (1)

1,000 mg/L SO4 2.5 mL 125 mg/L SO4/41.8 mg/L S (2)

10,000 mg/L Ca 50 μL 25 mg/L Ca

2% HNO3 to 20 mL (or 20 g)

Cal. Standard 7 Stock solution Volume (μL) Final concentration (μg/L)

(SO4 and PO4 High) 1,000 mg/L PO4 5 mL 250 mg/L PO4/81.6 mg/L P (1)

1,000 mg/L SO4 5 mL 250 mg/L SO4/83.6 mg/L S (2)

10,000 mg/L Ca 50 μL 25 mg/L Ca

2% HNO3 to 20 mL (or 20 g)

Note 1: 1,000 mg/L PO4 is equivalent to 326.4 mg/L P

Note 2: 1,000 mg/L SO4 is equivalent to 334.4 mg/L S
11

Safety Precautions

All laboratory personnel are required to wear safety glasses, gloves, closed toe shoes, and lab 

coats when working in the laboratory. Refer to the laboratory chemical hygiene plan and material safety 

data sheets (MSDSs) for specific precautions, effects of overexposure, and first-aid treatment for 

reagents used in the preparation procedure and operation of the ICP-MS system.

Sample Preparation

Samples need to be preserved with HNO3 to a pH ≤2 at sample collection or as soon as possible 

after sample collection. Most sampling protocols require that the samples are filtered and acidified in the 

field (Wanty and others, 1999; Wilde and others, 2004; U.S. Geological Survey, 2006). At the analyst’s 

discretion, unfiltered samples collected as raw acidified (RA) may be filtered or decanted prior to 

analysis if visible particulates or solids are present to prevent clogging of the sample introduction 

system (for example, sample probe or nebulizer). Samples with conductivities greater than 1,500 μS/cm 

are generally diluted by the analyst in 2 percent HNO3 using a suitable dilution factor to bring the 

conductivity down to <1,500 μS/cm in order to prevent clogging of the sample introduction system and 

minimize matrix interferences. The analyst should notify the sample submitter if this or any other 

procedures were necessary to analyze the samples. If the sample results are over the calibration curve, 

dilution and reanalysis of the affected samples for the over range elements is required or a high-level 

standard at a concentration above the highest measured sample level is analyzed with results within 5 

percent of the true or prepared value. 

Procedure

After a 30-minute warm-up time, the ICP-MS instrument is optimized to meet manufacturer or 

USGS-specific operating parameters, including Autolens and dual-detector calibration according to the 

instructions in the ELAN version 3.4 ICP-MS software. The instrument is then calibrated using the 

standard solutions listed in table 5, and the operating parameters shown in table 6. The operating 

parameters may vary slightly depending on the specific model ICP-MS, nebulizer, and spray chamber 

being used for analysis. 

The ICP-MS is calibrated using a blank and the seven standards listed in table 5 at the beginning 

of each analytical session using a linear through zero calibration equation. The calibration blank should 

be prepared from the same source and at the same acid concentration used in the calibration standards. 

Blank subtraction is performed to negate the effect of the reagents when the blank is higher than the 

detection limit. The accuracy of the method is checked using a minimum of three aqueous quality 

control samples such as certified reference materials (CRMs) from the National Institutes for Standards 

and Technology (NIST, http://www.nist.gov) and various other reference materials suppliers or 

Standard Reference Samples (SRSs) available from the USGS Standard Reference Sample Project 

(http://bqs.usgs.gov/srs/). 
12

Table 6. ELAN DRC-e operating parameters. 

[RF, radio frequency; W, watts; L/min, liters per minute; mm, millimeter; rpm, rotations per minute; i.d., internal diameter; s, 

seconds; ms, milliseconds]

Instrument parameter Setting or type

RF power 1350W

Cool gas (L/min) 18

Auxilary gas (L/min) 1.5

Nebulizer gas (L/min) 0.78 – 0.82

Injector 2 mm quartz

Spray chamber Cyclonic, quartz, Peltier-cooled (PC3, ESI, Inc., Omaha, Neb.)

Pump Speed 10 rpm

Pump Tubing Orange-orange (0.89 mm i.d.)

Uptake Rate 1 mL/min (sample and internal standard lines together)

Integration time (ms) 10 – 100 milliseconds

Nebulizer Meinhard Concentric, Type TR-50-C1 (Meinhard, Inc., Golden, Colo.)

Rinse time (s) 90 seconds at 10 rpm

Specific method name HP_Waters.mth

Before running unknown samples, the calibration is verified using one or more independent 

calibration verification (ICV) standards that are prepared from a stock originating from a different 

supplier than the stock(s) used to prepare the calibration standards. The ICV solution should be prepared 

at a level near the mid-point of each the calibration curve for each element. To verify calibrations for all 

57 elements present in the calibration solutions, three separate ICV solutions are typically used—see 

table 7. The measured ICV concentrations must be within ±10 percent of the true or prepared value. If 

the ICV results are not within acceptable limits, then the source of the error should be identified and 

corrected and the instrument recalibrated and the ICV solution(s) reanalyzed. Common errors include 

improperly prepared calibration standards or stock solutions and inadequate mixing of the internal 

standard solution with the sample solutions. The results for all quality control sample (CRM or SRS) 

analyses should be within ±20 percent of the certified or proposed values, including stated errors. If the 

results are not within ±20 percent of the stated values, the samples are prepared again and reanalyzed by 

ICP-MS. If the results are still not within acceptable values, the instrument and method parameters are 

checked and the instrument is recalibrated using freshly prepared calibration standards and the quality 

control samples are reanalyzed. For every 10 unknown samples, a blank, continuous calibration 

verification (CCV), and a quality control sample are analyzed. The CCV solution(s) are prepared from 

the same stock standards used to prepare the calibration standards and may be one or more of the 

calibration standards reanalyzed to verify continuing calibration accuracy. The measured CCV 

concentrations should be within ±10 percent of the true or prepared value. If the CCV values are not 

within limits, the instrument and method parameters are checked and the instrument is recalibrated 

using freshly prepared calibration standards and any affected quality control and unknown samples are 

reanalyzed. If the quality control sample is not within ±20 percent of the accepted value, the instrument 

and method parameters are checked and the instrument is recalibrated using freshly prepared calibration 

standards, and any affected quality control and unknown samples are reanalyzed. 
13

Table 7. Preparation and final concentration of independent calibration verification standards for Inductively 

Coupled Plasma-Mass Spectrometry (ICP-MS) analysis. 

[μg/L, microgram per liter; mg/L, milligram per liter; %, percent; mL, milliliter; μL, microliter; g, gram; mg, milligram] 

I.V. ICV-75 Stock solution Volume (μL) Final concentration (μg/L)

ICV Stock 1A (IV-ICPMS-71A) 150 μL 75 μg/L (all elements)

ICV Stock 1B (IV-ICPMS-71B) 150 μL 75 μg/L (all elements)

Second Source Water Matrix Stock 2 mL 25 mg/L Na, Ca; 5 mg/L Mg, K, Si

2% HNO3 to 20 mL (or 20 g)

PE ICV-75 Stock solution Volume (μL) Final concentration (μg/L)

ICV Stock 2A (N9300233) 150 μL 75 μg/L (all elements)

ICV Stock 2B (N9300232) 150 μL 75 μg/L (all elements)

ICV Stock 2C (N9300235) 150 μL 75 μg/L (all elements)

Second Source Water Matrix Stock 2 mL 25 mg/L Na, Ca; 5 mg/L Mg, K, Si

2% HNO3 to 20 mL (or 20 g)

P-S ICV-50 Stock solution Volume (μL) Final concentration (μg/L)

(SO4 and PO4 ICV) Second Source 1000 mg/L PO4 3.0 mL 150 mg/L PO4/49.0 mg/L P

Second Source 1000 mg/L SO4 3.0 mL 150 mg/L SO4/50.2 mg/L S

10,000 mg/L Ca 50 μL 25 mg/L Ca

2% HNO3 to 20 mL (or 20 g)

Method Performance—Blank Analysis and Reporting Limits

The instrument detection limits and reporting limits calculated from more than 40 blank analyses 

are shown in table 8. The preferred masses for reporting are selected based on background equivalent 

concentration (BEC), achieved detection limits, analytical performance of quality control samples, and 

minimal interferences at the particular mass for a particular sample matrix. For some elements, more 

than one mass is analyzed in order to rule out possible interferences in unusual samples. Prior to 

reporting, the results for Si and S are converted to SiO2 and SO4 using 2.139 and 2.995 conversion 

factors, respectively. In table 8, the method detection limit (MDL) is calculated as a value equaling three 

times the standard deviation (SD) of a large number (n > 40) of blank analyses during a 3-month period. 

The lower reporting limit in table 8 is established by rounding the calculated MDL to a suitable number 

of significant figures and raising reporting levels for ubiquitous elements based on professional 

judgment to prevent false positives. The instrument MDLs and reporting limits are reevaluated on an 

annual basis or as instrument operating parameters are changed. The upper reporting limit is generally 

extended to two times the highest calibration standard. For samples with results reading above the 

highest calibration standard, either a quality control sample at a higher level or a high-level calibration 

standard can be used to verify linearity above the highest calibration concentration. 
14

Table 8. Blanks analysis, method detection limits, and reporting limits. 

[μg/L, microgram per liter; mg/L, milligram per liter; SD, standard deviation; MDL, method detection limit] 

Element Mass Calibration

units

Number

of

samples

Mean

Standard 

deviation 

(SD)

MDL = 3 x 

SD

Reporting 

limit

(μg/L)

Upper 

reporting limit 

(1)

Li 7 μg/L 42 –0.1243 0.8166 2.450 5 500

Be 9 μg/L 42 –0.0008 0.0066 0.020 0.05 500

Na 23 mg/L 42 0.0026 0.0122 0.037 0.05 100

Na-1 23 mg/L 42 0.0025 0.0122 0.036 0.05 100

Na-2 23 mg/L 42 0.0027 0.0136 0.041 0.05 100

Mg 25 mg/L 42 0.0004 0.0030 0.009 0.01 20

Al 27 μg/L 42 0.3403 0.7442 2.233 3 500

Al-1 27 μg/L 42 0.4815 0.7503 2.251 3 500

Si (2) 29 mg/L 42 0.0419 0.0670 0.201 0.2 40

P 31 mg/L 42 0.0022 0.0032 0.009 0.01 200

S (3) 34 mg/L 42 0.5845 1.6279 4.884 5 200

K 39 mg/L 42 0.0039 0.0065 0.019 0.03 20

Ca 43 mg/L 42 0.0002 0.0234 0.070 0.2 100

Ca 44 mg/L 42 0.0024 0.0105 0.032 0.2 100

Sc 45 μg/L 42 0.0358 0.1111 0.333 0.6 500

Ti 49 μg/L 42 –0.0024 0.0473 0.142 0.5 500

V 51 μg/L 42 –0.0012 0.0237 0.071 0.5 500

Cr 52 μg/L 42 0.0060 0.0913 0.274 1 500

Cr 53 μg/L 42 0.0185 0.2494 0.748 1 500

Fe 54 μg/L 42 3.1744 6.6543 19.963 60 500

Mn 55 μg/L 42 –0.0014 0.0074 0.022 0.2 500

Fe 57 μg/L 42 –4.7339 19.6910 59.073 60 500

Ni 58 μg/L 42 –0.0374 0.0896 0.269 0.3 500

Co 59 μg/L 42 0.0001 0.0011 0.003 0.4 500

Ni 60 μg/L 42 –0.0125 0.0739 0.222 0.4 500

Cu 63 μg/L 42 –0.0030 0.0128 0.038 0.5 500

Zn 66 μg/L 42 0.0359 0.0619 0.186 1 500

Ga 71 μg/L 42 –0.0002 0.0027 0.008 0.05 500

Ge 74 μg/L 42 0.0002 0.0038 0.011 0.05 500

As-1 75 μg/L 42 –0.0229 0.0654 0.196 1 500

As 75 μg/L 42 –0.0042 0.0264 0.079 1 500

Se 77 μg/L 42 0.0800 0.2186 0.656 1 500

Se 82 μg/L 42 –0.0059 0.1515 0.455 1 500

Rb 85 μg/L 42 0.0010 0.0018 0.005 0.01 500

Sr 88 μg/L 42 0.0096 0.0191 0.057 0.5 500

Y 89 μg/L 42 0.0002 0.0008 0.002 0.01 500

Zr 90 μg/L 42 0.0021 0.0031 0.009 0.2 500

Nb 93 μg/L 42 0.0100 0.0097 0.029 0.2 500
15

Table 8. Blanks analysis, method detection limits, and reporting limits.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; SD, standard deviation; MDL, method detection limit]

Element Mass Calibration

units

Number

of

samples

Mean

Standard 

deviation 

(SD)

MDL = 3 x 

SD

Reporting 

limit

(μg/L)

Upper 

reporting limit 

(1)

Mo 98 μg/L 42 –0.0225 0.0901 0.270 2 500

Ag 109 μg/L 42 –0.0501 0.0884 0.265 1 500

Cd 114 μg/L 42 0.0003 0.0011 0.003 0.02 500

Sb 121 μg/L 42 0.0188 0.0178 0.053 0.3 500

Cs 133 μg/L 42 0.0009 0.0010 0.003 0.02 500

Ba 135 μg/L 42 0.0036 0.0127 0.038 0.2 500

La 139 μg/L 42 0.0003 0.0007 0.002 0.01 500

Ce 140 μg/L 42 0.0002 0.0008 0.002 0.01 500

Pr 141 μg/L 42 0.0004 0.0005 0.002 0.01 500

Nd 146 μg/L 42 0.0008 0.0015 0.004 0.01 500

Sm 149 μg/L 42 0.0008 0.0017 0.005 0.01 500

Eu 151 μg/L 42 0.0003 0.0008 0.002 0.005 500

Tb 159 μg/L 42 0.0003 0.0006 0.002 0.005 500

Gd 160 μg/L 42 0.0006 0.0012 0.004 0.005 500

Dy 164 μg/L 42 0.0002 0.0014 0.004 0.005 500

Ho 165 μg/L 42 0.0004 0.0006 0.002 0.005 500

Er 166 μg/L 42 –0.0002 0.0010 0.003 0.005 500

Tm 168 μg/L 42 0.0002 0.0005 0.002 0.005 500

Yb 172 μg/L 42 –0.0001 0.0013 0.004 0.01 500

Lu 175 μg/L 42 0.0002 0.0004 0.001 0.1 500

Ta 181 μg/L 42 0.0150 0.0130 0.039 0.05 500

W 184 μg/L 42 0.0320 0.0278 0.084 0.5 500

Tl 205 μg/L 42 0.0064 0.0073 0.022 0.1 500

Pb 208 μg/L 42 0.0005 0.0034 0.010 0.05 500

Bi 209 μg/L 42 0.0033 0.0045 0.013 0.2 500

Th 232 μg/L 42 0.0019 0.0019 0.006 0.2 500

U 238 μg/L 42 0.0000 0.0009 0.003 0.1 500

(1) Upper limit is based on 2 times the highest calibration standard. Samples higher than this should be verified by 

running a check standard higher than the highest reading sample(s).

(2) multiply by 2.139 to report as SiO2

(3) multiply by 2.995 factor to report as SO4
16

Method Performance—Analyses of Quality Control Samples

Results obtained for repeated analyses of six quality control samples analyzed by this method 

(T–131, T–201, T–207, T–175, M–158, and PPREE) are summarized in table 9. These samples, in 

addition to ICV samples discussed in the ICP-MS analyses section, are used to check the method 

performance during analyses of unknown samples that range from pristine natural waters to mine waste

waters and various geologic sample leachates—samples that vary greatly in concentrations of trace and 

major elements. The six quality control samples shown in this report represent trace and major elements 

in natural waters collected at various locations in Colorado in which the trace and major constituents are 

modified (USGS Standard Reference Sample Project [http://bqs.usgs.gov/srs/]). The accepted or most 

probable value (MPV) for element concentrations in the USGS Standard Reference Sample (SRS) 

waters are determined via multilaboratory round-robin analysis. For many elements in the USGS SRSs, 

the levels are near the detection limits and are useful for evaluating accuracy at low concentrations. The 

PPREE sample is a standard reference water sample developed using mine water collected in the 

western San Juan Mountains, Colo. (Verplanck and others, 2001) that has elevated levels of Al, Ca, Fe, 

Mg, Mn, Sr, and rare earth elements. Many of the interferences discussed in Appendix 1 affect accurate 

determination of these elements, and the obtained concentrations listed in table 9 are within ±20 percent 

of the accepted value for most elements in this quality control sample. 

Table 9. Analysis of quality control samples. 

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation] 

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Silver, Ag μg/L

T-131 trace constituents 29 1.149 0.34 1.26 91%

T-201 trace constituents 34 17.75 4.11 17.30 103%

T-207 trace constituents 18 < 1 NA 0.05 NA

M-194 major constituents 27 < 1 NA NA NA

M-198 major constituents 33 < 1 NA NA NA

M-202 major constituents 23 < 1 NA NA NA

PPREE-1 trace constituents 10 < 1 NA NA NA

SCREE-1 trace constituents 10 < 1 NA NA NA

Aluminum, Al μg/L

T-131 trace constituents 29 128 7.00 132 97%

T-201 trace constituents 34 77.7 5.40 77.8 100%

T-207 trace constituents 14 320 12.0 324 99%

M-194 major constituents 27 < 3 NA NA NA

M-198 major constituents 33 < 3 NA NA NA

M-202 major constituents 23 < 3 NA NA NA

PPREE-1 trace constituents 10 12180 600 11500 106%

SCREE-1 trace constituents 10 12600 650 11200 113%
17

Table 9. Analysis of quality control samples.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation]

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Arsenic, As μg/L

T-131 trace constituents 29 56.8 1.30 56.6 100%

T-201 trace constituents 34 26.4 0.70 24.4 108%

T-207 trace constituents 13 0.98 0.08 0.87 114%

M-194 major constituents 27 < 0.3 NA NA NA

M-198 major constituents 33 < 0.3 NA NA NA

M-202 major constituents 23 < 0.3 NA NA NA

PPREE-1 trace constituents 10 1.5 0.30 1.5 100%

SCREE-1 trace constituents 10 < 0.3 NA 0.2 NA

Barium, Ba μg/L

T-131 trace constituents 29 523 47 507 103%

T-201 trace constituents 34 45.6 3.20 44.7 102%

T-207 trace constituents 13 43.6 1.67 42.9 102%

M-194 major constituents 27 41.1 8.70 NA NA

M-198 major constituents 33 14.4 2.70 NA NA

M-202 major constituents 23 14.8 0.40 NA NA

PPREE-1 trace constituents 10 7.49 0.38 7.10 106%

SCREE-1 trace constituents 10 37.6 1.30 34.5 109%

Beryllium, Be μg/L

T-131 trace constituents 29 12.2 0.90 12.2 100%

T-201 trace constituents 34 8.29 0.74 8.35 99%

T-207 trace constituents 13 0.084 0.02 0.09 92%

M-194 major constituents 27 < 0.05 NA NA NA

M-198 major constituents 33 < 0.05 NA NA NA

M-202 major constituents 23 < 0.05 NA NA NA

PPREE-1 trace constituents 10 1.97 0.33 2.50 79%

SCREE-1 trace constituents 10 < 0.5 NA 0.4 NA

Bismuth, Bi μg/L

T-131 trace constituents 29 14.4 1.13 NA NA

T-201 trace constituents 34 < 0.2 0.01 NA NA

T-207 trace constituents 18 < 0.2 0.00 NA NA

M-194 major constituents 27 < 0.2 0.02 NA NA

M-198 major constituents 32 < 0.2 0.01 NA NA

M-202 major constituents 22 < 0.2 0.01 NA NA

PPREE-1 trace constituents 10 < 0.2 0.00 NA NA

SCREE-1 trace constituents 10 < 0.2 0.00 NA NA
18

Table 9. Analysis of quality control samples.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation]

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Calcium, Ca mg/L

T-131 trace constituents 29 31.6 1.50 30.6 103%

T-201 trace constituents 34 53.7 2.70 53.1 101%

T-207 trace constituents 18 23.5 1.10 23.4 100%

M-194 major constituents 27 23.3 5.50 24.4 95%

M-198 major constituents 32 10.2 0.61 10.4 98%

M-202 major constituents 22 5.5 0.20 5.6 98%

PPREE-1 trace constituents 10 481 56.3 NA NA

SCREE-1 trace constituents 10 95.6 9.50 NA NA

Cadmium, Cd μg/L

T-131 trace constituents 29 6.6 0.34 6.1 108%

T-201 trace constituents 34 16.7 0.57 15.7 106%

T-207 trace constituents 18 0.63 0.03 0.59 107%

M-194 major constituents 27 < 0.02 0.01 NA NA

M-198 major constituents 32 < 0.02 0.00 NA NA

M-202 major constituents 22 < 0.02 0.00 NA NA

PPREE-1 trace constituents 10 0.5 0.02 NA NA

SCREE-1 trace constituents 10 12.5 0.39 NA NA

Cerium, Ce μg/L

T-131 trace constituents 29 0.01 0.01 NA NA

T-201 trace constituents 34 2.8 0.28 NA NA

T-207 trace constituents 18 3.8 0.14 NA NA

M-194 major constituents 27 < 0.01 0.01 NA NA

M-198 major constituents 32 < 0.01 0.01 NA NA

M-202 major constituents 22 < 0.01 0.01 NA NA

PPREE-1 trace constituents 10 181 7.20 161 112%

SCREE-1 trace constituents 10 26.3 1.20 24.6 107%

Cobalt, Co μg/L

T-131 trace constituents 29 26.3 0.75 24.6 107%

T-201 trace constituents 34 18.1 0.73 17.4 104%

T-207 trace constituents 18 0.95 0.03 0.98 97%

M-194 major constituents 27 < 0.02 0.00 NA NA

M-198 major constituents 32 < 0.02 0.00 NA NA

M-202 major constituents 22 < 0.02 0.00 NA NA

PPREE-1 trace constituents 10 114 7.80 NA NA

SCREE-1 trace constituents 10 35.2 1.50 NA NA
19

Table 9. Analysis of quality control samples.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation]

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Chromium, Cr μg/L

T-131 trace constituents 29 19.5 0.61 18.6 105%

T-201 trace constituents 34 35.2 1.50 33.7 104%

T-207 trace constituents 18 < 1 0.10 NA NA

M-194 major constituents 27 < 1 0.10 NA NA

M-198 major constituents 32 2 0.50 NA NA

M-202 major constituents 22 < 1 0.10 NA NA

PPREE-1 trace constituents 10 < 1 0.20 NA NA

SCREE-1 trace constituents 10 < 1 0.20 NA NA

Cesium, Cs μg/L

T-131 trace constituents 29 4.8 0.41 NA NA

T-201 trace constituents 34 0.22 0.01 NA NA

T-207 trace constituents 18 0.5 0.02 NA NA

M-194 major constituents 27 < 0.02 0.00 NA NA

M-198 major constituents 32 < 0.02 0.00 NA NA

M-202 major constituents 22 < 0.02 0.00 NA NA

PPREE-1 trace constituents 10 1.4 0.05 NA NA

SCREE-1 trace constituents 10 0.18 0.01 NA NA

Copper, Cu μg/L

T-131 trace constituents 29 21.9 1.20 20.2 108%

T-201 trace constituents 34 22 1.10 20.8 106%

T-207 trace constituents 18 10.1 1.70 8.4 120%

M-194 major constituents 27 < 0.5 0.05 NA NA

M-198 major constituents 32 < 0.5 0.04 NA NA

M-202 major constituents 22 < 0.5 0.10 NA NA

PPREE-1 trace constituents 10 1.4 0.07 NA NA

SCREE-1 trace constituents 10 817 21.9 NA NA

Iron, Fe μg/L

T-131 trace constituents 29 63.8 33.3 90.7 70%

T-201 trace constituents 34 1990 195 1810 110%

T-207 trace constituents 18 463 26.1 432 107%

M-194 major constituents 27 < 50 48.0 NA NA

M-198 major constituents 32 < 50 27.6 NA NA

M-202 major constituents 22 < 50 5.00 NA NA

PPREE-1 trace constituents 10 88600 6370 NA NA

SCREE-1 trace constituents 10 4850 179 NA NA
20

Table 9. Analysis of quality control samples.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation]

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Gallium, Ga μg/L

T-131 trace constituents 29 < 0.05 NA NA NA

T-201 trace constituents 34 0.08 0.02 NA NA

T-207 trace constituents 18 0.08 0.01 NA NA

M-194 major constituents 27 < 0.05 NA NA NA

M-198 major constituents 32 < 0.05 NA NA NA

M-202 major constituents 22 < 0.05 NA NA NA

PPREE-1 trace constituents 10 1.5 0.10 NA NA

SCREE-1 trace constituents 10 0.31 0.02 NA NA

Gadolinium, Gd μg/L

T-131 trace constituents 29 < 0.005 NA NA NA

T-201 trace constituents 34 0.34 0.04 NA NA

T-207 trace constituents 18 0.27 0.03 NA NA

M-194 major constituents 27 < 0.005 NA NA NA

M-198 major constituents 32 < 0.005 NA NA NA

M-202 major constituents 22 < 0.005 NA NA NA

PPREE-1 trace constituents 10 29.7 1.90 23.8 125%

SCREE-1 trace constituents 10 10.6 0.73 8.2 129%

Germanium, Ge μg/L

T-131 trace constituents 29 0.1 0.00 NA NA

T-201 trace constituents 34 < 0.05 NA NA NA

T-207 trace constituents 18 < 0.05 NA NA NA

M-194 major constituents 27 < 0.05 NA NA NA

M-198 major constituents 32 < 0.05 NA NA NA

M-202 major constituents 22 < 0.05 NA NA NA

PPREE-1 trace constituents 10 0.37 0.02 NA NA

SCREE-1 trace constituents 10 0.1 0.10 0.1 100%

Holmium, Ho μg/L

T-131 trace constituents 29 < 0.005 NA NA NA

T-201 trace constituents 34 0.057 0.01 NA NA

T-207 trace constituents 18 0.04 0.00 NA NA

M-194 major constituents 27 < 0.005 NA NA NA

M-198 major constituents 32 < 0.005 NA NA NA

M-202 major constituents 22 < 0.005 NA NA NA

PPREE-1 trace constituents 10 5 0.40 4.4 114%

SCREE-1 trace constituents 10 1.9 0.19 1.6 119%
21

Table 9. Analysis of quality control samples.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation]

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Potassium, K mg/L

T-131 trace constituents 29 2.4 0.16 2.4 100%

T-201 trace constituents 34 5.2 0.32 5.2 99%

T-207 trace constituents 18 2.2 0.11 2.2 100%

M-194 major constituents 27 3.1 0.60 3.3 94%

M-198 major constituents 32 1.4 0.10 1.5 97%

M-202 major constituents 22 1.3 0.05 1.3 99%

PPREE-1 trace constituents 10 0.97 0.11 NA NA

SCREE-1 trace constituents 10 5.6 0.45 NA NA

Lanthanum, La μg/L

T-131 trace constituents 29 0.02 0.00 NA NA

T-201 trace constituents 34 1.7 0.18 NA NA

T-207 trace constituents 18 1.7 0.08 NA NA

M-194 major constituents 27 < 0.01 < 0.01 NA NA

M-198 major constituents 32 < 0.01 < 0.01 NA NA

M-202 major constituents 22 < 0.01 < 0.01 NA NA

PPREE-1 trace constituents 10 86.4 3.61 80.4 110%

SCREE-1 trace constituents 10 10.6 0.44 9.8 110%

Lithium, Li μg/L

T-131 trace constituents 29 16.4 1.67 17 100%

T-201 trace constituents 34 27.3 1.60 27.9 100%

T-207 trace constituents 18 21.5 2.47 22.2 100%

M-194 major constituents 27 2.5 0.80 NA NA

M-198 major constituents 32 0.4 0.70 NA NA

M-202 major constituents 22 0.3 1.20 NA NA 

PPREE-1 trace constituents 10 1.1 0.30 NA NA

SCREE-1 trace constituents 10 9 2.61 NA NA

Lutetium, Lu μg/L

T-131 trace constituents 29 < 0.1 NA NA NA

T-201 trace constituents 34 < 0.1 NA NA NA

T-207 trace constituents 18 < 0.1 NA NA NA

M-194 major constituents 27 < 0.1 NA NA NA

M-198 major constituents 32 < 0.1 NA NA NA

M-202 major constituents 22 < 0.1 NA NA NA

PPREE-1 trace constituents 10 1.3 0.05 1.1 110%

SCREE-1 trace constituents 10 0.5 0.04 0.5 110%
22

Table 9. Analysis of quality control samples.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation]

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Magnesium, Mg mg/L

T-131 trace constituents 29 8.2 0.59 8 100%

T-201 trace constituents 34 22.9 1.30 23.8 96%

T-207 trace constituents 18 6.2 0.23 6.2 99%

M-194 major constituents 27 5.8 1.30 6.2 93%

M-198 major constituents 32 4.4 0.47 4.8 92%

M-202 major constituents 22 1.5 0.07 1.5 96%

PPREE-1 trace constituents 10 36.7 1.80 NA NA

SCREE-1 trace constituents 10 27.1 1.39 NA NA

Manganese, Mn μg/L

T-131 trace constituents 29 38.4 2.85 37.8 100%

T-201 trace constituents 34 1810 135 1800 100%

T-207 trace constituents 18 237 9.19 237 100%

M-194 major constituents 27 4 0.87 NA NA

M-198 major constituents 32 3.5 0.40 NA NA

M-202 major constituents 22 6.8 0.20 NA NA

PPREE-1 trace constituents 10 6240 610 NA NA

SCREE-1 trace constituents 10 1760 118 NA NA

Molybdenum, 

Mo

μg/L

T-131 trace constituents 29 115 3.03 112 103%

T-201 trace constituents 34 29 0.98 30.5 95%

T-207 trace constituents 18 4.6 0.20 4.6 100%

M-194 major constituents 27 < 2 NA NA NA

M-198 major constituents 32 < 2 NA NA NA

M-202 major constituents 22 < 2 NA NA NA

PPREE-1 trace constituents 10 < 2 NA NA NA

SCREE-1 trace constituents 10 < 2 NA NA NA

Sodium, Na mg/L

T-131 trace constituents 29 21.9 1.11 21.4 100%

T-201 trace constituents 34 46.2 2.88 47.6 97%

T-207 trace constituents 18 21.9 2.16 21.5 100%

M-194 major constituents 27 23.5 5.00 25 94%

M-198 major constituents 32 8.9 0.56 9.4 94%

M-202 major constituents 22 7.5 0.68 7.4 100%

PPREE-1 trace constituents 10 10 1.71 NA NA

SCREE-1 trace constituents 10 14.1 2.26 NA NA
23

Table 9. Analysis of quality control samples.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation]

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Niobium, Nb μg/L

T-131 trace constituents 29 < 0.2 NA NA NA

T-201 trace constituents 34 < 0.2 NA NA NA

T-207 trace constituents 18 < 0.2 NA NA NA

M-194 major constituents 27 < 0.2 NA NA NA

M-198 major constituents 32 < 0.2 NA NA NA

M-202 major constituents 22 < 0.2 NA NA NA

PPREE-1 trace constituents 10 < 0.2 NA NA NA

SCREE-1 trace constituents 10 < 0.2 NA NA NA

Neodymium, Nd μg/L

T-131 trace constituents 29 < 0.01 NA NA NA

T-201 trace constituents 34 1.3 0.13 NA NA

T-207 trace constituents 18 1.9 0.09 NA NA

M-194 major constituents 27 < 0.01 NA NA NA

M-198 major constituents 32 < 0.01 NA NA NA

M-202 major constituents 22 < 0.01 NA NA NA

PPREE-1 trace constituents 10 106 4.35 92.3 120%

SCREE-1 trace constituents 10 26.5 1.40 22.1 120%

Nickel, Ni μg/L

T-131 trace constituents 29 60.3 1.66 56.3 110%

T-201 trace constituents 34 66.8 2.93 64 100%

T-207 trace constituents 18 1.9 0.24 1.7 110%

M-194 major constituents 27 0.7 0.22 NA NA

M-198 major constituents 32 < 0.4 < 0.4 NA NA

M-202 major constituents 22 < 0.4 0.00 NA NA

PPREE-1 trace constituents 10 20.4 0.848 NA NA

SCREE-1 trace constituents 10 13.3 0.53 NA NA

Phosphorus, P mg/L

T-131 trace constituents 29 < 0.01 NA NA NA

T-201 trace constituents 34 < 0.01 NA NA NA

T-207 trace constituents 18 0.02 0.005 NA NA

M-194 major constituents 27 0.3 0.08 0.3 100%

M-198 major constituents 32 0.2 0.00 0.2 100%

M-202 major constituents 22 0.02 0.01 0.02 70%

PPREE-1 trace constituents 10 0.06 0.00 NA NA

SCREE-1 trace constituents 10 < 0.01 0.00 NA NA
24

Table 9. Analysis of quality control samples.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation]

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Lead, Pb μg/L

T-131 trace constituents 29 19.4 1.48 18.1 107%

T-201 trace constituents 34 76.4 6.91 73.9 103%

T-207 trace constituents 18 4.96 0.22 4.8 103%

M-194 major constituents 27 < 0.05 0.06 NA NA

M-198 major constituents 32 < 0.05 NA NA NA

M-202 major constituents 22 < 0.05 NA NA NA

PPREE-1 trace constituents 10 0.19 0.01 NA NA

SCREE-1 trace constituents 10 13.4 0.49 NA NA

Praseodymium, 

Pr

μg/L

T-131 trace constituents 29 < 0.01 NA NA NA

T-201 trace constituents 34 0.34 0.03 NA NA

T-207 trace constituents 18 0.48 0.02 NA NA

M-194 major constituents 27 < 0.01 NA NA NA

M-198 major constituents 32 < 0.01 NA NA NA

M-202 major constituents 22 < 0.01 NA NA NA

PPREE-1 trace constituents 10 22.7 0.86 21.2 110%

SCREE-1 trace constituents 10 4.7 0.25 4.3 110%

Rubidium, Rb μg/L

T-131 trace constituents 29 12.1 0.37 NA NA

T-201 trace constituents 34 5.2 0.18 NA NA

T-207 trace constituents 18 6.2 0.26 NA NA

M-194 major constituents 27 1.4 0.22 NA NA

M-198 major constituents 32 0.62 0.06 NA NA

M-202 major constituents 22 0.65 0.02 NA NA

PPREE-1 trace constituents 10 2.8 0.11 NA NA

SCREE-1 trace constituents 10 7.1 0.21 NA NA

Sulfate, SO4 mg/L

T-131 trace constituents 29 < 2 1.11 NA NA

T-201 trace constituents 33 187.3 13.8 NA NA

T-207 trace constituents 18 44 3.63 NA NA

M-194 major constituents 27 15 3.95 16 94%

M-198 major constituents 32 9.6 2.11 10 96%

M-202 major constituents 22 5.1 0.88 4.4 116%

PPREE-1 trace constituents 10 1200 51.64 NA NA

SCREE-1 trace constituents 10 440 21.08 NA NA
25

Table 9. Analysis of quality control samples.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation]

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Antimony, Sb μg/L

T-131 trace constituents 29 56 4.05 56.2 100%

T-201 trace constituents 34 15.9 0.74 15.8 101%

T-207 trace constituents 18 < 0.3 NA NA NA

M-194 major constituents 27 < 0.3 NA NA NA

M-198 major constituents 32 < 0.3 0.142 NA NA

M-202 major constituents 22 < 0.3 NA NA NA

PPREE-1 trace constituents 10 < 0.3 NA NA NA

SCREE-1 trace constituents 10 < 0.3 NA NA NA

Scandium, Sc μg/L

T-131 trace constituents 29 0.6 0.06 NA NA

T-201 trace constituents 34 1.3 0.22 NA NA

T-207 trace constituents 18 0.7 0.08 NA NA

M-194 major constituents 27 1.2 0.29 NA NA

M-198 major constituents 32 0.8 0.13 NA NA

M-202 major constituents 22 < 0.6 NA NA NA

PPREE-1 trace constituents 10 2.3 0.14 NA NA

SCREE-1 trace constituents 10 4.7 0.35 NA NA

Selenium, Se μg/L

T-131 trace constituents 29 12.1 0.43 11.2 110%

T-201 trace constituents 34 10.5 0.50 9 120%

T-207 trace constituents 18 < 1 0.04 NA NA

M-194 major constituents 27 < 1 0.70 NA NA

M-198 major constituents 32 < 1 0.13 NA NA

M-202 major constituents 22 2.3 0.55 NA NA

PPREE-1 trace constituents 10 1.7 0.29 NA NA

SCREE-1 trace constituents 10 2.3 0.32 NA NA

Silicon Dioxide, 

SiO2

mg/L

T-131 trace constituents 29 6.4 0.49 5.8 100%

T-201 trace constituents 33 13 0.93 13 100%

T-207 trace constituents 18 7.9 0.32 8.1 100%

M-194 major constituents 27 13 2.35 13 100%

M-198 major constituents 32 7.8 0.73 7.6 100%

M-202 major constituents 22 5.8 0.20 6.2 90%

PPREE-1 trace constituents 10 28 1.71 NA NA

SCREE-1 trace constituents 10 38 1.08 NA NA
26

Table 9. Analysis of quality control samples.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation]

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Samarium, Sm μg/L

T-131 trace constituents 29 < 0.01 NA NA NA

T-201 trace constituents 33 0.27 0.03 NA NA

T-207 trace constituents 18 0.34 0.02 NA NA

M-194 major constituents 27 < 0.01 NA NA NA

M-198 major constituents 32 < 0.01 NA NA NA

M-202 major constituents 22 < 0.01 NA NA NA

PPREE-1 trace constituents 10 23.1 0.95 20.3 110%

SCREE-1 trace constituents 10 8 0.52 6.7 120%

Strontium, Sr μg/L

T-131 trace constituents 29 297 16 295 100%

T-201 trace constituents 33 397 21 396 100%

T-207 trace constituents 18 157 5.87 161 97%

M-194 major constituents 25 129 13 135 95%

M-198 major constituents 32 47.9 4.28 52.4 91%

M-202 major constituents 22 36 1.32 37.4 96%

PPREE-1 trace constituents 10 2850 128 NA NA

SCREE-1 trace constituents 10 123 3.93 NA NA

Tantalum, Ta μg/L

T-131 trace constituents 29 < 0.02 0.01 NA NA

T-201 trace constituents 33 < 0.02 0.01 NA NA

T-207 trace constituents 18 < 0.02 NA NA NA

M-194 major constituents 27 < 0.02 NA NA NA

M-198 major constituents 32 0.03 0.02 NA NA

M-202 major constituents 22 < 0.02 NA NA NA

PPREE-1 trace constituents 10 < 0.02 NA NA NA

SCREE-1 trace constituents 10 < 0.02 NA NA NA

Terbium, Tb μg/L

T-131 trace constituents 29 < 0.005 NA NA NA

T-201 trace constituents 33 0.05 0.01 NA NA

T-207 trace constituents 18 0.04 0.00 NA NA

M-194 major constituents 27 < 0.005 NA NA NA

M-198 major constituents 32 < 0.005 NA NA NA

M-202 major constituents 22 < 0.005 NA NA NA

PPREE-1 trace constituents 10 4 0.28 3.6 110%

SCREE-1 trace constituents 10 1.5 0.12 1.3 110%
27

Table 9. Analysis of quality control samples.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation]

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Thorium, Th μg/L

T-131 trace constituents 29 < 0.2 NA NA NA

T-201 trace constituents 33 < 0.2 NA NA NA

T-207 trace constituents 18 < 0.2 NA NA NA

M-194 major constituents 27 < 0.2 NA NA NA

M-198 major constituents 32 < 0.2 NA NA NA

M-202 major constituents 22 < 0.2 NA NA NA

PPREE-1 trace constituents 10 < 0.2 NA NA NA

SCREE-1 trace constituents 10 < 0.2 NA NA NA

Titanium, Ti μg/L

T-131 trace constituents 29 < 0.5 NA NA NA

T-201 trace constituents 33 3.7 0.71 NA NA

T-207 trace constituents 18 7 0.31 NA NA

M-194 major constituents 27 < 0.5 NA NA NA

M-198 major constituents 32 < 0.5 NA NA NA

M-202 major constituents 22 < 0.5 NA NA NA

PPREE-1 trace constituents 10 13.7 0.45 NA NA

SCREE-1 trace constituents 10 5.1 0.27 NA NA

Thallium, Tl μg/L

T-131 trace constituents 29 8 0.58 NA NA

T-201 trace constituents 33 6.82 0.59 6.32 108%

T-207 trace constituents 18 0.51 0.02 0.48 106%

M-194 major constituents 27 < 0.1 NA NA NA

M-198 major constituents 32 < 0.1 NA NA NA

M-202 major constituents 22 < 0.1 NA NA NA

PPREE-1 trace constituents 10 < 0.1 NA NA NA

SCREE-1 trace constituents 10 0.73 0.03 NA NA

Thulium, Tm μg/L

T-131 trace constituents 29 < 0.005 NA NA NA

T-201 trace constituents 33 0.02 0.00 NA NA

T-207 trace constituents 18 0.01 0.00 NA NA

M-194 major constituents 27 < 0.005 NA NA NA

M-198 major constituents 32 < 0.005 NA NA NA

M-202 major constituents 22 < 0.005 NA NA NA

PPREE-1 trace constituents 10 1.7 0.15 1.5 110%

SCREE-1 trace constituents 10 0.66 0.06 0.58 110%
28

Table 9. Analysis of quality control samples.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation]

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Uranium, U μg/L

T-131 trace constituents 29 < 0.1 NA NA NA

T-201 trace constituents 33 9.56 1.11 9.22 104%

T-207 trace constituents 18 1.87 0.10 1.8 104%

M-194 major constituents 27 1.65 0.47 NA NA

M-198 major constituents 32 0.2 0.04 NA NA

M-202 major constituents 22 0.17 0.01 NA NA

PPREE-1 trace constituents 10 0.13 0.007 NA NA

SCREE-1 trace constituents 10 0.28 0.02 NA NA

Vanadium, V μg/L

T-131 trace constituents 29 36.8 1.18 34.2 110%

T-201 trace constituents 33 29.2 1.33 28.4 100%

T-207 trace constituents 18 0.9 0.06 NA NA

M-194 major constituents 27 2.7 0.18 2.8 100%

M-198 major constituents 32 6.4 0.41 6.6 100%

M-202 major constituents 22 < 0.5 NA NA NA

PPREE-1 trace constituents 10 1.8 0.25 NA NA

SCREE-1 trace constituents 10 < 0.5 NA NA NA

Tungsten, W μg/L

T-131 trace constituents 29 < 0.5 NA NA NA

T-201 trace constituents 33 < 0.5 NA NA NA

T-207 trace constituents 18 < 0.5 NA NA NA

M-194 major constituents 27 < 0.5 NA NA NA

M-198 major constituents 32 < 0.5 0.54 NA NA

M-202 major constituents 22 < 0.5 NA NA NA

PPREE-1 trace constituents 10 < 0.5 NA NA NA

SCREE-1 trace constituents 10 < 0.5 NA NA NA

Yttrium, Y μg/L

T-131 trace constituents 29 < 0.01 NA NA NA

T-201 trace constituents 33 2 0.07 NA NA

T-207 trace constituents 18 1 0.05 NA NA

M-194 major constituents 27 < 0.01 NA NA NA

M-198 major constituents 32 < 0.01 NA NA NA

M-202 major constituents 22 < 0.01 NA NA NA

PPREE-1 trace constituents 10 140 0.279 NA NA

SCREE-1 trace constituents 10 45.1 1.40 NA NA
29

Table 9. Analysis of quality control samples.—Continued

[μg/L, microgram per liter; mg/L, milligram per liter; NA, not applicable; n, number; %, percent; SD, standard deviation]

Quality Contol

Sample Description n 

Average 

determined

value

SD Accepted 

value % Recovery

Ytterbium, Yb μg/L

T-131 trace constituents 29 < 0.01 NA NA NA

T-201 trace constituents 33 0.1 0.01 NA NA

T-207 trace constituents 18 0.07 0.01 NA NA

M-194 major constituents 27 < 0.01 NA NA NA

M-198 major constituents 32 < 0.01 NA NA NA

M-202 major constituents 22 < 0.01 NA NA NA

PPREE-1 trace constituents 10 9.5 0.59 NA NA

SCREE-1 trace constituents 10 4 0.26 NA NA

Zinc, Zn ug/L

T-131 trace constituents 29 75 3.26 72 104%

T-201 trace constituents 33 1200 54 1110 108%

T-207 trace constituents 18 225 7.75 200 113%

M-194 major constituents 27 4.3 0.58 NA NA

M-198 major constituents 32 < 3 NA NA NA

M-202 major constituents 22 < 3 0.06 NA NA

PPREE-1 trace constituents 10 586 34 NA NA

SCREE-1 trace constituents 10 2030 72 NA NA

Zirconium, Zr μg/L

T-131 trace constituents 29 < 0.2 NA NA NA

T-201 trace constituents 33 < 0.2 0.08 NA NA

T-207 trace constituents 18 < 0.2 0.06 NA NA

M-194 major constituents 27 < 0.2 NA NA NA

M-198 major constituents 32 < 0.2 NA NA NA

M-202 major constituents 22 < 0.2 NA NA NA

PPREE-1 trace constituents 10 < 0.2 NA NA NA

SCREE-1 trace constituents 10 < 0.2 NA NA NA

References Cited

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high signals: Shelton, Conn., PerkinElmer, Inc., Field Application Report #007437_01, 3 p., accessed 

July 7, 2014, at http://perkinelmer.co.kr/files/AP00155.pdf.

Allain, Pierre, Jaunalt, Laurent, Mauras, Yves, Mermet, Jean Michel, and Delaporte, Thierry, 1991, 

Signal enhancement of elements due to the presence of carbon-containing compounds in inductively 

coupled plasma mass spectrometry: Analytical Chemistry, v. 63, no. 14, p. 1497–1498. 

Horlick, Gary, and Montaser, Akbar, 1998, Analytical characteristics of ICP-MS in inductively coupled 

plasma mass spectrometry (Montaser, Akbar, ed.): New York, New York, United States, Wiley-VCH, 

Inc., ISBN 0-0471-18620-1, p. 503–588. 
30

Jarvis, K.E., Gray, A.L., and Houk, R.S., 1992, Handbook of Inductively Coupled Plasma Mass 

Spectrometry: Glasgow, Scotland, United Kingdom, Blackie and Son Ltd., ISBN 0-216-92912-1, p 

125–152. 

Kralj, Polonca, and Veber, Marjan, 2003, Investigations into nonspectroscopic effects of organic 

compounds inductively coupled plasma mass spectrometry: Acta Chimica Slovenica, v. 50, p. 633–

644. 

Lichte, F.E., Meier, A.L., and Crock, J.G., 1987, Determination of the rare earth elements in geological 

materials by inductively coupled plasma mass spectrometry: Analytical Chemistry, v. 59, no. 8, p. 

1150–1157. 

Olesik, J.W., and Bates, L.C., 1995, Characterization of aerosols produced by pneumatic nebulizers for 

inductively coupled plasma sample introduction—Effect of liquid and gas flow rates on volume based 

drop size distributions: Spectrochimica Acta, v. 50B, nos. 4–7, p. 285–303. 

Tanner, S.D., and Baranov, V.I., 1999, A dynamic reaction cell for inductively coupled plasma mass 

spectrometry (ICPDRC-MS)—Part II—Reduction of interferences produced within the cell: Journal 

of the American Society of Mass Spectrometry, v. 10, p. 1083–1094. 

Tanner, S.D., Baranov, V.I., and Bandura, D.R., 2002, Reaction cells and collision cells for ICP-MS—

A tutorial review: Spectrochimica Acta Part B, v. 57, p. 1361–1452. 

U.S. Environmental Protection Agency, 2007a, SW–846—Test methods for evaluating solid waste, 

physical/chemical methods, Method 3015A, microwave assisted acid digestion of aqueous samples 

and extracts: U.S. Environmental Protection Agency, revision 1, February 2007, accessed June 25, 

2014, at http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/3015a.pdf. 

U.S. Environmental Protection Agency, 2007b, SW–846—Test methods for evaluating solid waste, 

physical/chemical methods, Method 6020A, inductively coupled plasma mass spectrometry: U.S. 

Environmental Protection Agency, revision 1, February 2007, accessed July 7, 2014, at

http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/6020a.pdf.

U.S. Geological Survey, 2006, Collection of water samples (ver. 2.0): U.S. Geological Survey 

Techniques of Water-Resources Investigations, book 9, chap. A4, September 2006, accessed January 

6, 2014, at http://pubs.water.usgs.gov/twri9A4/. 

Verplanck, P. L., Antweiler, R. C., Nordstrom, D. K., Taylor, H. E., 2001, Standard reference water 

samples for rare earth element determinations: Applied Geochemistry, v. 16, p. 231-244. 

Wanty, R.B., Wang, Bronwen, Vohden, Jim, Briggs, P.H., and Meier, A.H., 1999, Regional baseline 

geochemistry and environmental effects of gold placer mining operations on the Fortymile River, 

eastern Alaska: U.S. Geological Survey Open-File Report 99–328, p. 11. 

Wilde, F.D., Radtke, D.B., Gibs, Jacob, and Iwatsubo, R.T., eds., 2004–2009, Processing of water 

samples (ver. 2.2): U.S. Geological Survey Techniques of Water-Resources Investigations, book 9, 

chap. A5, April 2004, accessed July 7, 2014, at http://pubs.water.usgs.gov/twri9A5/. 

Wolf, R.E., Denoyer, Eric, and Grosser, Zoe, 2001, U.S. EPA Method 200.8 for the analysis of drinking 

waters and wastewaters: PerkinElmer Instruments, ICP-MS Application Note D–6527, Second 

Edition, accessed July 7, 2014, at http://perkinelmer.co.kr/files/AP00031.pdf. 

ISSN 2331-1258 (online)

http://dx.doi.org/10.3133/ofr20151010
31

Appendix 1. Determination of Empirical Oxide Corrections

For the rare earth elements (REEs), elements affected by high levels of Ca in samples such as 

Fe, Ni, and Co, and for the correction of 91Zr16O and 93Nb16O interferences on 107Ag and 109Ag, 

respectively; empirical oxide correction equations are used that must be reevaluated on a routine basis 

as instrument tuning parameters are changed. Before performing oxide corrections, optimize the 

instrument and record the CeO/Ce ratio from the Daily Performance Report. If operating parameters 

result in a CeO/Ce ratio more than 50 percent different than when the corrections were previously 

evaluated, the oxide corrections should be redetermined. The instrumental parameters for determining 

oxide corrections are given in table 1–1. 

Table 1–1. Elements and timing parameters for oxide interference correction determination.

[cps, counts per second; MCA, multichannel analyzer; ms, milliseconds]

Number of Sweeps: 15

Number of Replicates: 3

Element Mass Scan mode MCA

channels

Dwell time 

(ms)

Integration 

time (ms)

Ca 42.9588 Peak Hopping 1 50 750

Ca 43.9555 Peak Hopping 1 50 750

Fe 56.9354 Peak Hopping 1 50 750

Ni 57.9353 Peak Hopping 1 50 750

Co 58.9332 Peak Hopping 1 50 750

Ni 59.9332 Peak Hopping 1 50 750

Ni 60.931 Peak Hopping 1 50 750

Zr 89.9043 Peak Hopping 1 50 750

Nb 92.906 Peak Hopping 1 50 750

Mo 94.9058 Peak Hopping 1 50 750

Mo 97.9055 Peak Hopping 1 50 750

Ag 106.905 Peak Hopping 1 50 750

Ag 108.905 Peak Hopping 1 50 750

Cd 110.904 Peak Hopping 1 50 750

Cd 113.904 Peak Hopping 1 50 750

Ba 134.906 Peak Hopping 1 50 750

Ba 137.905 Peak Hopping 1 50 750

La 138.906 Peak Hopping 1 50 750

Ce 139.905 Peak Hopping 1 50 750

Pr 140.907 Peak Hopping 1 50 750

Nd 142.91 Peak Hopping 1 50 750

Nd 145.913 Peak Hopping 1 50 750

Sm 146.915 Peak Hopping 1 50 750

Sm 148.917 Peak Hopping 1 50 750

Eu 150.92 Peak Hopping 1 50 750

Eu 152.929 Peak Hopping 1 50 750
32

Table 1–1. Elements and timing parameters for oxide interference correction determination.

[cps, counts per second; MCA, multichannel analyzer; ms, milliseconds]

Number of Sweeps: 15

Number of Replicates: 3

Element Mass Scan mode MCA

channels

Dwell time 

(ms)

Integration 

time (ms)

Gd 157.924 Peak Hopping 1 50 750

Tb 158.925 Peak Hopping 1 50 750

Gd 159.927 Peak Hopping 1 50 750

Dy 160.927 Peak Hopping 1 50 750

Dy 163.929 Peak Hopping 1 50 750

Ho 164.93 Peak Hopping 1 50 750

Er 165.93 Peak Hopping 1 50 750

Tm 168.934 Peak Hopping 1 50 750

Yb 171.937 Peak Hopping 1 50 750

Yb 172.938 Peak Hopping 1 50 750

Lu 174.941 Peak Hopping 1 50 750

Hf 178.946 Peak Hopping 1 50 750

Hf 179.947 Peak Hopping 1 50 750

Ta 180.948 Peak Hopping 1 50 750

W 183.951 Peak Hopping 1 50 750

Procedure for Determining Oxide Corrections

1. Create a quantitative method using the isotopes and timing parameters given in table 1–1. Be 

sure to go into the Equations tab in the Method Editor and delete ALL correction equations. 

Save the method under a suitable name such as Oxide Corrections.mth. The resulting data 

can either be printed or sent to an electronic file.

2. Prepare single element solutions of the following elements at a concentration of 10 

micrograms per liter (μg/L)—Zr, Nb, Mo, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, 

Tm, Yb, Lu, Hf, Ta, and W; A 50 milliliter (mL) volume of each is sufficient for several 

analyses.

3. Prepare a single element solution of calcium (Ca) at 10 milligram per liter (mg/L); a 50 mL 

volume is sufficient for several analyses.

4. Prepare 50 mL of 2 percent nitric acid (HNO3) using double-distilled nitric acid and 18 

megaohm (MΩ) deionized water to be used as a blank solution. 

5. Set up the autosampler to run a minimum of 5 blanks initially, followed by a single analysis 

of each individual element solution with two blanks in between each solution. A washout 

time of at least two minutes between each solution is recommended to prevent carryover 

effects. 

6. Once the solutions are analyzed, enter the resulting intensities for the blanks and each

individual element solution into the shaded areas of the oxide correction calculations 

spreadsheet in table 1–2. The basis for calculating the correction equations is to calculate the 

ratio of the apparent signal for each interfering element at the interfered with element’s mass 
33

to the net intensity of the interfering element. This correction ratio is then multiplied by the 

measured intensity of each interfering element measured in the sample solutions to adjust for 

changing concentrations of the interfering elements. Whenever possible, choose masses to 

measure the interfering element signals that do not contain interferences. The equations used 

to perform calculations are shown in table 1–2. All formulas for table 1–2 are available in a 

downloadable Microsoft Excel file at http://pubs.usgs.gov/of/2015/1010/pdf/ofr2015-

1010_table1-2.xlsx. Collected data are entered into the appropriate blank fields and the 

calculations are performed automatically.

7. The spreadsheet in table 1–2 contains sections for elements where there are multiple 

interfering elements affecting an analyte mass. The correction equations for the first section, 

called First Order Corrections, for the REEs are calculated and then entered into the 

analytical method used to collect the data and the raw data reprocessed for the elements 

contained in the next set of REE correction equations, called Second Order Corrections in 

table 1–2. The resulting corrected raw data are then entered into the second area of the 

spreadsheet to generate the Second Order Corrections. The second order corrections are then 

entered into the analytical method in addition to any first order corrections and the data 

reprocessed again to generate the corrected raw data for generation of the Third Order 

Corrections in the third area of the spreadsheet. At each step, the analyst will review the 

results for the corrected raw data to ensure the corrections are resulting in signals for the 

interference-affected elements near the background levels observed in the blank solution 

analyses.

8. The corrections in the Other Oxide corrections area of the spreadsheet in table 1–2 can be 

generated along with the First Order Corrections, because these are not interrelated to the 

rare earth element oxide corrections.

9. The correction equations generated in the spreadsheet in table 1–2 must be saved, recorded, 

and entered into every individual method where these correction equations should be 

utilized. Note that the ELAN Instrument Control software offers no capability for correction 

equations to be automatically updated in multiple methods.
34

Table 1–2. Correction equations calculation worksheet with formulas used for calculations shown. [cps, counts per second] 

A B C D E F G H I J K L M M O P

1 

First Order

Corrections

interfering

element

Blank

(cps)

Blank

(cps)

Average blank

(cps)

Hi

standard

(cps)

Net

intensity

for

element

Interfered

with

element

Blank 

(cps)

Blank 

(cps)

Average blank

(cps)

Apparent

Element

Intensity

(cps)

Net 

apparent 

element 

intensity 

(cps)

Calculated 

correction

Interfering 

element Correction to enter

2 Ba135 =AVERAGE(B2:C2) =E2-D2 Eu151 =AVERAGE(H2:I2) =K2-J2 =L2/F2 =G2 =-1*M2 ="*"&A2

3 Ba135 =AVERAGE(B3:C3) =E3-D3 Nd146 =AVERAGE(H3:I3) =K3-J3 =L3/F3 =G3 =-1*M3 ="*"&A3

4 Nd146 =AVERAGE(B4:C4) =E4-D4 Tb159 =AVERAGE(H4:I4) =K4-J4 =L4/F4 =G4 =-1*M4 ="*"&A4

5 Sm149 =AVERAGE(B5:C5) =E5-D5 Ho165 =AVERAGE(H5:I5) =K5-J5 =L5/F5 =G5 =-1*M5 ="*"&A5

6 Eu151 =AVERAGE(B6:C6) =E6-D6 Tm169 =AVERAGE(H6:I6) =K6-J6 =L6/F6 =G6 =-1*M6 ="*"&A6

7 Eu151 =AVERAGE(B7:C7) =E7-D7 Er166 =AVERAGE(H7:I7) =K7-J7 =L7/F7 =G7 =-1*M7 ="*"&A7

8 Gd160 =AVERAGE(B8:C8) =E8-D8 Yb172 =AVERAGE(H8:I8) =K8-J8 =L8/F8 =G8 =-1*M8 ="*"&A8

9 Gd160 =AVERAGE(B9:C9) =E9-D9 Yb173 =AVERAGE(H9:I9) =K9-J9 =L9/F9 =G9 =-1*M9 ="*"&A9

10 Ho165 =AVERAGE(B10:C10) =E10-D10 Ta181 =AVERAGE(H10:I10) =K10-J10 =L10/F10 =G10 =-1*M10 ="*"&A10

11 Er166 =AVERAGE(B11:C11) =E11-D11 W184 =AVERAGE(H11:I11) =K11-J11 =L11/F11 =G11 =-1*M11 ="*"&A11

12 Ta181 =AVERAGE(B12:C12) =E12-D12 Hf180 =AVERAGE(H12:I12) =K12-J12 =L12/F12 =G12 =-1*M12 ="*"&A12

13 Dy164 =AVERAGE(B13:C13) =E13-D13 Gd160 =AVERAGE(H13:I13) =K13-J13 =L13/F13 =G13 =-1*M13 ="*"&A13

14 Er166 =AVERAGE(B14:C14) =E14-D14 Dy164 =AVERAGE(H14:I14) =K14-J14 =L14/F14 =G14 =-1*M14 ="*"&A14

15 Nd146 =AVERAGE(B15:C15) =E15-D15 Er166 =AVERAGE(H15:I15) =K15-J15 =L15/F15 =G15 =-1*M15 ="*"&A15

16 Dy164 =AVERAGE(B16:C16) =E16-D16 Hf179 =AVERAGE(H16:I16) =K16-J16 =L16/F16 =G16 =-1*M16 ="*"&A16

17 Gd160 =AVERAGE(B17:C17) =E17-D17 Lu175 =AVERAGE(H17:I17) =K17-J17 =L17/F17 =G17 =-1*M17 ="*"&A17

18 END FIRST ORDER CORRECTIONS – PUT THESE IN AND REPROCESS DATA FOR SECOND ORDER CORRECTION ELEMENTS LISTED BELOW

19

20 2ND ORDER CORRECTION ELEMENTS

21 Nd146 =AVERAGE(B21:C21) =E21-D21 Gd160 =AVERAGE(H21:I21) =K21-J21 =L21/F21 =G21 =-1*M21 ="*"&A21

22 Nd146 =AVERAGE(B22:C22) =E22-D22 Dy164 =AVERAGE(H22:I22) =K22-J22 =L22/F22 =G22 =-1*M22 ="*"&A22

23 Sm149 =AVERAGE(B23:C23) =E23-D23 Er166 =AVERAGE(H23:I23) =K23-J23 =L23/F23 =G23 =-1*M23 ="*"&A23

24 END SECOND ORDER CORRECTIONS – PUT THESE IN AND REPROCESS DATA FOR THIRD ORDER CORRECTION ELEMENTS LISTED BELOW

25

26 THIRD ORDER CORRECTION ELEMENTS

27 Sm149 =AVERAGE(B27:C27) =E27-D27 Gd160 =AVERAGE(H27:I27) =K27-J27 =L27/F27 =G27 =-1*M27 ="*"&A27

28 Sm149 =AVERAGE(B28:C28) =E28-D28 Dy164 =AVERAGE(H28:I28) =K28-J28 =L28/F28 =G28 =-1*M28 ="*"&A28

29 W184 =AVERAGE(B29:C29) =E29-D29 Hf180 =AVERAGE(H29:I29) =K29-J29 =L29/F29 =G29 =-1*M29 ="*"&A29

30 Dy164 =AVERAGE(B30:C30) =E30-D30 Hf180 =AVERAGE(H30:I30) =K30-J30 =L30/F30 =G30 =-1*M30 ="*"&A30

31 

32 

33 OTHER OXIDE CORRECTIONS

34 Ca43 =AVERAGE(B34:C34) =E34-D34 Fe57 =AVERAGE(H34:I34) =K34-J34 =L34/F34 =G34 =-1*M34 ="*"&A34

35 Ca43 =AVERAGE(B35:C35) =E35-D35 Co59 =AVERAGE(H35:I35) =K35-J35 =L35/F35 =G35 =-1*M35 ="*"&A35

36 Ca43 =AVERAGE(B36:C36) =E36-D36 Ni60 =AVERAGE(H36:I36) =K36-J36 =L36/F36 =G36 =-1*M36 ="*"&A36

37

38 Zr90 =AVERAGE(B38:C38) =E38-D38 Ag107 =AVERAGE(H38:I38) =K38-J38 =L38/F38 =G38 =-1*M38 ="*"&A38

39 Nb93 =AVERAGE(B39:C39) =E39-D39 Ag109 =AVERAGE(H39:I39) =K39-J39 =L39/F39 =G39 =-1*M39 ="*"&A39

40

41 Mo 95 =AVERAGE(B41:C41) =E41-D41 Cd 111 =AVERAGE(H41:I41) =K41-J41 =L41/F41 =G41 =-1*M41 ="*"&A41

42 Mo 98 =AVERAGE(B42:C42) =E42-D42 Cd 114 =AVERAGE(H42:I42) =K42-J42 =L42/F42 =G42 =-1*M42 ="*"&A42