Geochemical Data for Samples Collected in 2008 Near the … · 2009-12-07 · Geochemical Data for...

U.S. Department of the InteriorU.S. Geological Survey

Open-File Report 2009–1239

Geochemical Data for Samples Collected in 2008 Near the Concealed Pebble Porphyry Cu-Au-Mo Deposit, Southwest Alaska

Report cover illustration: View to NE of Pebble deposit area from vicinity of Frying Pan Lake in July 2008. Photograph by David L. Fey.


By David L. Fey, Matthew Granitto, Stuart A. Giles, Steven M. Smith, Robert G. Eppinger, and Karen D. Kelley

Open-File Report 2009–1239

U.S. Department of the InteriorU.S. Geological Survey

U.S. Department of the Interior KEN SALAZAR, Secretary

U.S. Geological Survey Marcia K. McNutt, Director

U.S. Geological Survey, Reston, Virginia: 2009

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Suggested citation: Fey, D.L., Granitto, M., Giles, S.A., Smith, S.M., Eppinger, R.G., and Kelley, K.D., 2009, Geochemical data for samples collected in 2008 near the concealed Pebble porphyry Cu-Au-Mo deposit, southwest Alaska: U.S. Geological Survey Open-File Report 2009-1239, 107 p., http://pubs.usgs.gov/of/2009/1239.

Any use of trade, product, or firm names is for descriptive purposes only and does not imply endorsement by the U.S. Government.

Although this report is in the public domain, permission must be secured from the individual copyright owners to reproduce any copyrighted material contained within this report.

iii

Contents

Introduction.....................................................................................................................................................1Cooperative Nature of the Study ........................................................................................................3Geologic Setting ....................................................................................................................................4Acknowledgements ..............................................................................................................................4

Sampling Methods .........................................................................................................................................4Water ......................................................................................................................................................4Solid Materials ......................................................................................................................................5

Soil ..................................................................................................................................................5Stream Sediment .........................................................................................................................5Pond Sediment .............................................................................................................................6Pond-sediment Core ....................................................................................................................6

Analytical Methods........................................................................................................................................6Water ......................................................................................................................................................6

Field Parameters ..........................................................................................................................6Laboratory analyses ....................................................................................................................6

Solid Materials ......................................................................................................................................6Soil Analyses ................................................................................................................................6Stream Sediment Analyses ........................................................................................................7Pond Surface and Core Sediment Analyses ...........................................................................7

Relational Database ......................................................................................................................................7Contents of Database ...........................................................................................................................8Database Structure ..............................................................................................................................8

Data Quality Control and Quality Assessment ........................................................................................11Sources of Geochemical Variation and Methods for Assuring Data Quality ...........................11Quality Assurance/Quality Control Methods ..................................................................................11Quality Control Samples ....................................................................................................................12Evaluation of Data Sets by Analytical Laboratory .........................................................................12

Skyline Assayers and Laboratories Enzyme Leach of Soils ...............................................13Skyline Assayers and Laboratories TerraSol Leach of Soils ..............................................13ALS Chemex Cold Hydroxylamine Hydrochloride Leach of Soils ......................................14ALS Chemex Ionic Leach of Soils ...........................................................................................14SGS Minerals Services (USGS Contract) Analysis of Soils, Sediments, and

Pond-sediment Cores ..................................................................................................14ICPAES–MS42 ...................................................................................................................15ICPAES–MS55 ...................................................................................................................16Various Single-Element Methods ...................................................................................16

Activation Laboratories, Ltd., High-Resolution ICP–MS Analysis of Waters ...................16USGS Laboratories Analysis of Waters .................................................................................17

Total/Ferrous Iron in Water by Ferrozine Analysis ......................................................17Dissolved Organic Carbon in Water by Combustion-Infrared Analysis ...................17Anions by Ion Chromatography and Alkalinity by Titration in Water Samples .......17

Summary and Conclusion of the Quality Control Evaluation for the Various Geochemical Data Sets ........................................................................................................18

References Cited..........................................................................................................................................18

iv

Appendix 1: Analytical Methods and Reporting Limits ..........................................................................20Appendix 2: Quality Control Tables and Charts for Skyline Assayers and Laboratories

Enzyme Leach Data ........................................................................................................................27Appendix 3: Quality Control Tables and Charts for Skyline Assayers and Laboratories

TerraSol Leach Data ......................................................................................................................36Appendix 4: Quality Control Tables and Charts for ALS Chemex Cold Hydroxylamine

Hydrochloride Leach Data ............................................................................................................46Appendix 5: Quality Control Tables and Charts for ALS Chemex Ionic Leach Data..........................54Appendix 6: Quality Control Tables and Charts for SGS Mineral Service (USGS contract)

Data: ICPAES–MS42 Multielement Package, ICPAES–MS55 Multielement Package, Forms of Carbon, and Selected Single Element Methods .......................................................61

Appendix 7: Quality Control Tables and Charts for Activation Laboratories, Ltd., High-Resolution ICP–MS Data .....................................................................................................96

Appendix 8: Quality Control Tables and Charts for Additional USGS Analytical Methods ............104

Figures

1. Location of the Pebble deposit study area, southwest Alaska. ............................................2 2. 2007 and 2008 sample traverses and outlines of Pebble East and

Pebble West zones .......................................................................................................................3 3. Tables in the relational database and the relationships between tables ...........................8 2-1. Precision plot for 14 analytical duplicate sample pairs by enzyme leach ........................29 2-2. Precision plot for six analyses of standard reference material QAlqt

by enzyme leach .........................................................................................................................32 2-3. Accuracy plot for six analyses of standard reference material QAlqt

by enzyme leach .........................................................................................................................32 2-4. Precision plot for six analyses of standard reference material QRd

by enzyme leach .........................................................................................................................35 2-5. Accuracy plot for six analyses of standard reference material QRd

by enzyme leach .........................................................................................................................35 3-1. Precision plot for 14 analytical duplicate sample pairs by TerraSol leach .......................38 3-2. Precision plot for six analyses of standard reference material QAlqt

by TerraSol leach ........................................................................................................................40 3-3. Precision plot for six analyses of standard reference material QRd

by TerraSol leach ........................................................................................................................43 3-4. Precision plot for three analyses of standard reference material PB–SNP

by TerraSol leach ........................................................................................................................45 4-1. Precision plot for five analytical duplicate sample pairs by cold

hydroxylamine leach ..................................................................................................................48 4-2. Precision plot for two analyses of standard reference material LK4–ALG

by cold hydroxylamine leach. ...................................................................................................50 4-3. Accuracy plot for two analyses of standard reference material LK4–ALG

by cold hydroxylamine leach ....................................................................................................51 4-4. Precision plot for eight analyses of Pebble project standard reference

material PB–SMM by cold hydroxylamine leach. .................................................................53 4-5. Accuracy plot for eight analyses of standard reference material PB–SMM

by cold hyroxylamine leach ......................................................................................................54

v

5-1. Precision plot for seven analyses of standard reference material ION–SRM18 by ionic leach .......................................................................................................56

5-2. Accuracy plot for seven analyses of standard reference material ION–SRM18 by ionic leach .......................................................................................................58

5-3. Precision plot for four analyses of standard reference material SAR–L by ionic leach .................................................................................................................58

5-4. Precision plot for 14 analyses of standard reference material PB–SMM by ionic leach ............................................................................................................60

6-1. Precision plot for eleven analytical duplicate sample pairs by ICPAES–MS42 .............................................................................................................................62

6-2. Precision plot for 10 analytical duplicate sample pairs by ICPAES–MS55 .......................64 6-3. Precision plot for 11 analytical duplicate sample pairs by single-element

methods ........................................................................................................................................65 6-4. Precision plot for seven analyses of USGS standard reference material

SAR–L by ICPAES–MS42 ...........................................................................................................67 6-5. Accuracy plot for seven analyses of USGS standard reference material

SAR–L by ICPAES–MS42. ..........................................................................................................67 6-6. Precision plot for seven analyses of USGS standard reference material

SAR–L by ICPAES–MS55 ...........................................................................................................69 6-7. Accuracy plot for seven analyses of USGS standard reference material

SAR–L by ICPAES–MS55 ...........................................................................................................70 6-8. Precision plot for seven analyses of USGS standard reference material

SAR–L by single-element methods ..........................................................................................71 6-9. Accuracy plot for seven analyses of USGS standard reference material

SAR–L by single-element methods ..........................................................................................71 6-10. Precision plot for eight analyses of USGS standard reference material

SAR–M by ICPAES–MS42 .........................................................................................................73 6-11. Accuracy plot for eight analyses of USGS standard reference material

SAR–M by ICPAES–MS42 .........................................................................................................73 6-12. Precision plot for eight analyses of USGS standard reference material

SAR–M by ICPAES–MS55 .........................................................................................................75 6-13. Accuracy plot for eight analyses of USGS standard reference material

SAR–M by ICPAES–MS55 .........................................................................................................76 6-14. Precision plot for eight analyses of USGS standard reference material

SAR–M by single-element methods ........................................................................................77 6-15. Accuracy plot for eight analyses of USGS standard reference material

SAR–M by single-element methods ........................................................................................77 6-16. Precision plot for three analyses of USGS standard reference material

DGPM by ICPAES–MS42 ...........................................................................................................79 6-17. Accuracy plot for three analyses of USGS standard reference material

DGPM by ICPAES–MS42 ...........................................................................................................79 6-18. Precision plot for three analyses of USGS standard reference material

DGPM by ICPAES–MS55 ...........................................................................................................81 6-19. Accuracy plot for three analyses of USGS standard reference material

DGPM by ICPAES–MS55 ...........................................................................................................82 6-20. Precision plot for three analyses of USGS standard reference material

DGPM by single-element methods ..........................................................................................83 6-21. Accuracy plot for three analyses of USGS standard reference material

DGPM by single-element methods ..........................................................................................83

vi

6-22. Precision plot for four analyses of USGS standard reference material GSP–QC by ICPAES–MS42 ........................................................................................................85

6-23. Accuracy plot for four analyses of USGS standard reference material GSP–QC by ICPAES–MS42 ........................................................................................................85

6-24. Precision plot for four analyses of USGS standard reference material GSP–QC by ICPAES–MS55 ........................................................................................................87

6-25. Accuracy plot for four analyses of USGS standard reference material GSP–QC by ICPAES–MS55 ........................................................................................................88

6-26. Precision plot for four analyses of USGS standard reference material GSP–QC by single-element methods .......................................................................................89

6-27. Accuracy plot for four analyses of USGS standard reference material GSP–QC by single-element methods .......................................................................................89

6-28. Precision plot for 20 analyses of Pebble project standard reference material PB–SMM by ICPAES–MS42 ......................................................................................................91

6-29. Accuracy plot for 20 analyses of Pebble project standard reference material PB–SMM by ICPAES–MS42 ......................................................................................................91

6-30. Precision plot for 20 analyses of Pebble project standard reference material PB–SMM by ICPAES–MS55 ......................................................................................................93

6-31. Accuracy plot for 20 analyses of Pebble project standard reference material PB–SMM by ICPAES–MS55 ......................................................................................................94

6-32. Precision plot for 20 analyses of Pebble project standard reference material PB–SMM by single-element methods. ...................................................................................95

6-33. Accuracy plot for 20 analyses of Pebble project standard reference material PB–SMM by single-element methods ....................................................................................95

7-1. Precision plot for three analyses of standard reference material NIST–1643e by High-Resolution ICP–MS ......................................................................................................98

7-2. Accuracy plot for three analyses of standard reference material NIST–1643e by High-Resolution ICP–MS ......................................................................................................98

7-3. Precision plot for four analyses of standard reference material T–159 by High-Resolution ICP–MS .........................................................................................................100

7-4. Accuracy plot for four analyses of standard reference material T–159 by High-Resolution ICP–MS. ........................................................................................................101

7-5. Precision plot for four analyses of standard reference material T–177 by High-Resolution ICP–MS .........................................................................................................103

7-6. Accuracy plot for four analyses of standard reference material T–177 by High-Resolution ICP–MS .........................................................................................................103

8-1. Precision plot for four analytical duplicate sample pairs for iron by ferrozine analysis and dissolved organic carbon (DOC) by combustion/infrared analysis .................................................................................................104

8-2. Precision plot for nine analytical duplicate sample pairs by ion chromatography and titration .................................................................................................105

8-3. Precision plot for seven analyses of USGS standard reference material M–158 by ion chromatography and titration ........................................................................106

8-4. Accuracy plot for seven analyses of USGS standard reference material M–158 by ion chromatography and titration ........................................................................107

vii

Tables

1. List of Pebble deposit spreadsheets .......................................................................................10 2. Summary of tables and charts in appendix 6, describing QC sample type,

analytical method, table numbers, and precision and accuracy chart numbers for solid samples analyzed by contract lab SGS Minerals for Pebble Project samples, 2008 ...................................................................................................15

1-1 Water analytical methods and reporting limits .....................................................................20 1-2. U.S. Geological Survey reporting limits for anions, alkalinity, dissolved

organic carbon, and ferrous iron .............................................................................................21 1-3a. Soil analytical methods and reporting limits ..........................................................................21 1-3b. Soil analytical methods and reporting limits ..........................................................................23 1-3c. Soil/sediment analytical methods and reporting limits ........................................................25 2-1. Summary statistics for assessing analytical variation on duplicate samples;

determined by an enzyme leach of soil samples at Skyline Labs .......................................27 2-2. Summary statistics for assessing analytical variation on the standard

reference material QAlqt; determined by an enzyme leach of soil samples at Skyline Labs ............................................................................................................................30

2-3. Summary statistics for assessing analytical variation on the standard reference material QRd; determined by an enzyme leach of soil samples at Skyline Labs ............................................................................................................................33

3-1. Summary statistics for assessing analytical variation on duplicate samples; determined by a TerraSol leach of soil samples at Skyline Labs .......................................36

3-2. Summary statistics for assessing analytical variation on the standard reference material QAlqt; determined by a TerraSol leach of soil samples at Skyline Labs ............................................................................................................................38

3-3. Summary statistics for assessing analytical variation on the standard reference material QRd; determined by a TerraSol leach of soil samples at Skyline Labs ............................................................................................................................41

3-4. Summary statistics for assessing analytical variation on the standard reference material PB–SNP; determined by a TerraSol leach of soil samples at Skyline Labs ............................................................................................................................43

4-1. Summary statistics for assessing analytical variation on duplicate samples; determined by a cold hydroxylamine hydrochloride leach of soil samples at ALS Chemex .................................................................................................................................46

4-2. Summary statistics for assessing analytical variation on the standard reference material LK4–ALG; determined by a cold hydroxylamine hydrochloride leach of soil samples at ALS Chemex ...........................................................48

4-3. Summary statistics for assessing analytical variation on the Pebble project standard reference material PB–SMM; determined by a cold hydroxylamine hydrochloride leach of soil samples at ALS Chemex ................................51

5-1. Summary statistics for assessing analytical variation on the standard reference material ION–SRM18; determined by an ionic leach of soil samples at ALS Chemex ............................................................................................................................54

5-2. Summary statistics for assessing analytical variation on the standard reference material SAR–L; determined by an ionic leach of soil samples at ALS Chemex .................................................................................................................................56

5-3. Summary statistics for assessing analytical variation on the standard reference material PB–SMM; determined by an ionic leach of soil samples at ALS Chemex ............................................................................................................................59

viii

6-1. Summary statistics for assessing analytical variation on duplicate samples; determined by a four-acid total digestion of soil samples by the ICPAES–MS42 multielement package at SGS Minerals ......................................................61

6-2. Summary statistics for assessing analytical variation on duplicate samples; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals ......................................................63

6-3. Summary statistics for assessing analytical variation on duplicate samples; determined by single-element methods at SGS Minerals ...................................................65

6-4. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–L; determined after a four-acid total digestion of soil samples by the ICPAES–MS42 multielement package at SGS Minerals ...................66

6-5. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–L; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals ..........................68

6-6. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–L; determined by various methods at SGS Minerals ................70

6-7. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–M; determined after a four-acid total digestion of soil samples by the ICPAES–MS42 multielement package at SGS Minerals ..........................72

6-8. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–M; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals. .........................74

6-9. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–M; determined by various methods at SGS Minerals ..............76

6-10. Summary statistics for assessing analytical variation on the USGS standard reference material DGPM; determined after a four-acid total digestion of soil samples by the ICPAES–MS42 multielement package at SGS Minerals ..........................78

6-11. Summary statistics for assessing analytical variation on the USGS standard reference material DGPM; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals. .........................80

6-12. Summary statistics for assessing analytical variation on the USGS standard reference material DGPM; determined by various methods at SGS Minerals ................82

6-13. Summary statistics for assessing analytical variation on the USGS standard reference material GSP–QC; determined after a four-acid total digestion of soil samples by the ICPAES–MS42 multielement package at SGS Minerals ..........................84

6-14. Summary statistics for assessing analytical variation on the USGS standard reference material GSP–QC; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals ..........................86

6-15. Summary statistics for assessing analytical variation on the USGS standard reference material GSP–QC; determined by various methods at SGS Minerals .............88

6-16. Summary statistics for assessing analytical variation on the Pebble project standard reference material PB–SMM; determined after a four-acid total digestion of soil, pond and stream sediment, and pond core sediment samples by the ICPAES–MS42 multielement package at SGS Minerals ..........................................90

6-17. Summary statistics for assessing analytical variation on the Pebble project standard reference material PB–SMM; determined after a sodium peroxide sinter of soil, pond and stream sediment, and pond core sediment samples by the ICPAES–MS55 multielement package at SGS Minerals ................................................92

ix

6-18. Summary statistics for assessing analytical variation on the Pebble project standard reference material PB–SMM; determined by various methods on soil, pond and stream sediment, and pond core sediment samples at SGS Minerals ..........................................................................................................94

7-1. Summary statistics for assessing analytical variation on the standard reference material NIST–1643e; determined by High-Resolution ICP–MS on water samples at Activation Laboratories, Ltd ................................................................96

7-2. Summary statistics for assessing analytical variation on the standard reference material T–159; determined by High-Resolution ICP–MS on water samples at Activation Laboratories, Ltd ......................................................................99

7-3. Summary statistics for assessing analytical variation on the standard reference material T–177; determined by High-Resolution ICP–MS on water samples at Activation Laboratories, Ltd ....................................................................101

8-1. Summary statistics for assessing analytical variation on duplicate samples; determined for iron by ferrozine analysis and dissolved organic carbon (DOC) by combustion/infrared analysis of water samples at the USGS .....................................104

8-2. Summary statistics for assessing analytical variation on duplicate samples pairs; determined on water samples by ion chromatography and titration at the USGS ....................................................................................................................................105

8-3. Summary statistics for assessing analytical variation on the USGS standard reference material M–158; determined on waters samples by ion chromatography and titration at the USGS ..........................................................................106

8-4. Accuracy plot for seven analyses of USGS standard reference material M–158 by ion chromatography and titration. RL is reporting limit ....................................107

x

Conversion Factors

Inch/Pound to SIMultiply By To obtain

Lengthfoot (ft) 0.3048 meter (m)mile (mi) 1.609 kilometer (km)yard (yd) 0.9144 meter (m)

Massounce, avoirdupois (oz) 28.35 gram (g) pound, avoirdupois (lb) 0.4536 kilogram (kg) ton, short (2,000 lb) 0.9072 megagram (Mg) ton, long (2,240 lb) 1.016 megagram (Mg)

SI to Inch/PoundMultiply By To obtain

Lengthmeter (m) 3.281 foot (ft) kilometer (km) 0.6214 mile (mi)meter (m) 1.094 yard (yd)

Massgram (g) 0.03527 ounce, avoirdupois (oz)kilogram (kg) 2.205 pound avoirdupois (lb)megagram (Mg) 1.102 ton, short (2,000 lb)megagram (Mg) 0.9842 ton, long (2,240 lb)

Temperature in degrees Celsius (°C) may be converted to degrees Fahrenheit (°F) as follows:

°F=(1.8×°C)+32

Temperature in degrees Fahrenheit (°F) may be converted to degrees Celsius (°C) as follows:

°C=(°F-32)/1.8

Vertical coordinate information is referenced to the World Geodetic System of 1984 (WGS84).

Horizontal coordinate information is referenced to the World Geodetic System of 1984 (WGS84).

Altitude, as used in this report, refers to distance above the vertical datum.

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).

Concentrations of chemical constituents in solid samples are given either percent (%), parts per million (ppm), or parts per billion (ppb).

xi

Introduction

In the summer of 2007, the U.S. Geological Survey (USGS) began an exploration geochemical research study near a porphyry copper-gold-molybdenum (Cu-Au-Mo) deposit in southwest Alaska referred to as the “Pebble” deposit. Field work continued in 2008. The Pebble deposit is extremely large and is almost entirely concealed by tundra, glacial deposits, and post-mineralization volcanic and volcaniclastic deposits. The deposit, comprised of the partially exposed Pebble West and the concealed Pebble East zones, is presently being explored by Pebble Limited Partnership (2009a).

The goals of the USGS study are: (1) to determine whether the known Pebble concealed deposit can be detected with surface samples, (2) to better understand the processes of metal migration from the deposit to the surface, and (3) to test and develop methods for assessing mineral resources in similar concealed terrains.1 The Pebble deposit was chosen for this study because it is concealed by surficial cover rocks, it is relatively undisturbed (except for exploration company drill holes), it is a large mineral system, and it is fairly well con-strained at depth by the drill hole geology and geochemistry.

The Pebble deposit is located in southwestern Alaska about 30 km (18 mi) northwest of the village of Iliamna and 320 km (200 mi) southwest of Anchorage (fig. 1). Elevations in the Pebble area range from 287 m (940 ft) at Frying Pan Lake just south of the deposit to 1,146 m (3,760 ft) on Kas-kanak Mountain about 5 km (3 mi) to the west. The deposit is in an area of relatively subdued topographic relief with an elevation of around 300 m (1,000 ft). This portion of Alaska is part of the subarctic regime mountains division, Yukon intermontane plateaus-tayga-meadow province ecoregion, as defined by Bailey (U.S. Forest Service, 2007).

1 The USGS undertakes unbiased, broad-scale mineral resource assessments of Federal lands to provide Congress and citizens with information on national mineral endowment. Research on known deposits is also done to refine and better constrain methods and deposit models for the mineral resource assess-ments. These goals aid in assessing mineral resource endowments on Federal lands.

Geochemical data for samples collected in 2007 are reported in Fey and others (2008). The present report presents analytical results for geochemical samples collected in 2008 from the Pebble deposit and surrounding areas. The analyti-cal data are presented digitally both as an integrated Microsoft 2003 Access® database and as Microsoft 2003 Excel® files.

During two 2008 sampling periods, July 07–20 and Sep-tember 20–24, USGS scientists collected soil, water, bedload stream sediment, bedload pond sediment, pond-sediment core, heavy-mineral concentrate, and till samples from the deposit area with the aid of helicopter support because the site currently lacks transportation infrastructure that allows ease of access. The sampling was undertaken during relatively dry and stable weather conditions. Only minor scattered rain showers occurred during the sampling periods, so surface con-ditions were largely unaffected by weather. The predominant sample media collected were soils, pond bedload sediments, and surface waters. This report contains the analytical results for the soil, water, stream and pond bedload sediment, and pond-sediment core samples.

In 2007, the project emphasis was on collecting soil samples along a transect across the deposit. Soils were sub-jected to a variety of partial extraction analytical techniques, to assess which techniques might provide useful elemental contrasts for geochemical detection of the concealed deposit. Water samples collected mostly from ponds and springs were also analyzed, as were vegetation samples. The emphasis for the 2008 field season was: (1) continued soil sampling along transects across the deposit, (2) sampling numerous ponds inside and outside of the deposit area for water and bedload sediment, (3) collecting stream sediment and water samples downstream of the deposit area, and (4) collecting glacial till samples. Glacial till samples were collected for mineralogical determination useful as geochemical anomaly indicators ini-tially in 2007; these were augmented with additional samples in 2008. Data from the till indicator mineral study, described in Kelley and others (2009), are not presented in this report.

In 2007, soil samples were collected along a single 7.8 km-long (4.8 mi) generally east-west traverse across the Pebble East and Pebble West zones (Fey and others, 2008). In July 2008,


By David L. Fey, Matthew Granitto, Stuart A. Giles, Steven M. Smith, Robert G. Eppinger, and Karen D. Kelley

2 Geochemical Data for Samples Collected Near the Concealed Pebble Porphyry Cu-Au-Mo Deposit, Southwest Alaska

additional soil samples were collected along a 4.5 km-long (2.8 mi) generally north-south traverse. This traverse crossed the Pebble East zone. In September 2008, soil samples were col-lected along three shorter traverses: an east-west traverse 1.3 km long (0.81 mi) over Pebble West, north of the 2007 line, to investigate a geophysical anomaly (Minsley and others, 2008); and along two traverses over a concealed deposit located some 14 km (8.7 mi) southwest of the Pebble deposit known as the 38 Occurrence. At the 38 Occurrence, soils were collected along a northeast-trending 1.1 km-long (0.7 mi) traverse and an intersecting northwest-trending 0.76 km-long (0.47 mi) traverse. Numerous pond-water and pond-sediment samples were col-lected over the greater Pebble deposit area to test whether these media are useful in detecting the deposit and to augment water samples collected in 2007. Stream sediment and stream water samples were collected downstream of the deposit area, along a 11.5 km (7.1 mi) reach of Talarik Creek and a 9.6 km (6.0 mi) reach of the Koktuli River to determine element disper-sion below the deposit. Finally, two 3-inch (7.6 cm) diameter

pond-sediment cores were collected from two ponds at Pebble West to determine element concentrations at depth in the pond sediment. Sample sites are shown on figure 2 and plate 1, and locality coordinates are provided in the accompanying Access and Excel files named FieldSite.

Water samples were analyzed for anions and alkalin-ity by USGS laboratories and for cations by high-resolution inductively coupled plasma–mass spectrometry (ICP–MS) by Activation Laboratories (Actlabs), as indicated in the section on the cooperative nature of the study. Soils and stream sedi-ments were analyzed for their total content by SGS Minerals Services under a contract with the USGS. Soil samples were also leached by four selected partial-extraction leaching pro-cedures and then analyzed by two commercial laboratories, as described in the following section.

Also included in this report are Au analyses by atomic absorption spectrophotometry following a fire assay pre-concentration, done on soil samples collected in 2007. Data quality assessment of the initial Au analyses for the 2007 soil

Iliamna

Anchorage

Kenai

Seward

Homer

PEBBLE

TYONEKQUAD

LIMEHILLSQUAD

LAKECLARKQUAD

ILIAMNAQUAD

SELDOVIAQUAD

KENAIQUAD SEWARD

QUAD

BLYINGSOUNDQUAD

DILLINGHAMQUAD

TAYLORMTNSQUAD

ANCHORAGEQUAD

COO

K

INLE

T

PACIFIC OCEAN

ILIAMNA LAKE

LAKECLARK

149°W150°W151°W152°W153°W154°W155°W156°W157°W

61°30'N

61°N

60°30'N

60°N

59°30'N

59°N

MAPAREA

ALASKA

KILOMETERS150

100500 MILES

100500

Figure 1. Location of the Pebble deposit study area, southwest Alaska.

Introduction 3

samples revealed analytical bias (Fey and other, 2008), so the samples were reanalyzed. These new analytical data are reported herein. Sample sites for the reanalyzed 2007 soil samples are shown on figure 2 and plate 1.

Cooperative Nature of the Study

The geochemical analyses included in this report and database are the result of a cooperative effort among the USGS and several commercial international geochemical labo-ratories, working under a Technical Assistance Agreement. For the soil samples, several partial leaching procedures were used. Some laboratories provided leaching techniques that are proprietary in nature, whereas others used techniques that are published. Specifically, the list below shows the laboratories

and the methods they contributed in the 2008 study. More details on the methods follow later in this report.

• Activation Laboratories, Ltd.—high-resolution ICP–MS analyses of water samples

• ALS Chemex—Ionic Leach and cold hydroxylamine leach of soil samples.

• SGS Minerals Services—contract analyses of near-total element concentrations of soil samples.

• Skyline Assayers and Laboratories—Enzyme leach and TerraSol leach of soil samples.

• USGS laboratories—soil pH, soil conductivity, and the following water analyses: ferrous iron, dissolved organic carbon, anion, and alkalinity.

Figure 2. 2007 and 2008 sample traverses and outlines of Pebble East and Pebble West zones.1

1 Copper equivalent (Cu eq.) ore zone contours are from Northern Dynasty Minerals, Ltd.

155°10'W155°20'W155°30'W

59°55'N

59°50'N

KILOMETERS151050

MILES1050

0.6% Cu eq. ore zone

0.3% Cu eq. ore zone

2007 sample site

2008 sample site

FryingPanLake

Groundhog Mt.

KoktuliMt.

Kaskanak Mt.

North Fork

Koktuli R.

Big WigglyLake

South Fork

Koktuli R.

Pebble Deposit

38 Occurrence Upper

Talar

ik

Creek

East Fork

SouthForkFlats


Geologic Setting

This information on the geologic setting of the Pebble deposit is summarized from Lang and others (2007) and from Northern Dynasty Minerals (2009). Pebble is a world-class Cu-Au-Mo porphyry deposit. The Pebble deposit consists of Pebble West, which was discovered by Cominco America in 1989, and Pebble East, which was discovered by Northern Dynasty Minerals, Ltd. (NDM) in 2005. Since 2001, NDM has explored the area, resulting in the discovery of Pebble East. In July 2007, NDM partnered with Anglo American in a 50-50 joint venture called the Pebble Limited Partnership (PLP). The combined West and East zones contain a resource of 72 billion pounds of Cu, 94 million ounces of Au, and 4.8 billion pounds of Mo (Measured, indicated, and inferred resources combined; Pebble Limited Partnership, 2009b).

Pebble is located in the Kahiltna terrane, south of the crustal-scale Lake Clark fault. Rocks in the Pebble district include gently folded Jurassic to Cretaceous argillite, siltstone, and wacke, cut by diorite sills, and intruded by intermediate to felsic Cretaceous igneous bodies. Pebble is hosted by satellite bodies of the Cretaceous Kaskanak Batholith.

Tundra-mantled, unconsolidated glacial cover ranges from 0 to 50 m (164 ft) in thickness. The Pebble West and Central zones extend from the surface to a depth of about 500 m (1,640 ft). The Pebble East zone is completely concealed and extends to at least 1,700 m (5,580 ft) depth. Pebble East was partly eroded and is covered by an eastward-thickening wedge of Paleocene to Eocene volcanic and sedimentary rocks, which are in turn covered by the glacial deposits. Min-eralized rocks show strong potassic alteration, dominated by K-feldspar and variable biotite. Sericitically-altered rocks are found on the margin of the deposit, but propylitic assemblages are only locally found. Ore minerals include chalcopyrite, molybdenite, and native gold, found mostly within chalcopy-rite, all in multigenerational quartz-carbonate-sulfide stock-work veins.

Acknowledgements

We are grateful to Northern Dynasty Minerals, Ltd., for allowing access onto the Pebble property, for logistical support while in the field, and for general encouragement in pursuing this research effort. In particular, we thank Mark Rebagliati (Geological Consulting), Lena Brommeland (NDM), and Jim Lang (Lang Geoscience, Inc.), and Nicola Struyk, Lindsey Kleppin, Brian McNulty, Robin Smith, Crystal Chung, and Miguel Ricardo for field assistance. We are also thankful to the following commercial analytical laboratories and associ-ated individuals for contributing analytical support under a formal Technical Assistance Agreement: Eric Hoffman, Activation Laboratories, Ltd. (www.actlabsint.com), S. Mary Doherty and Brenda Caughlin, ALS Chemex (www.alsche-mex.com), and J. Robert Clark, Skyline Assayers and Labora-tories (www.skylinelab.com). SGS Minerals Services (www.sgs.com) are thanked for providing geochemical analyses

under USGS contract. We also thank the following USGS scientists: Michael Anthony for anion and alkalinity analyses, and Richard O’Leary for assistance with data management. Reviews by Richard O’Leary and Douglas Yager improved the manuscript greatly.

Sampling Methods

Water

Water samples and field parameter measurements were collected at 81 sites (fig. 2 and plate 1). Water samples were collected from lakes, ponds, or groundwater sources either from within the deposit boundaries, or from more distant locations. Sample site duplicates of all water aliquots were collected at four sites for quality assurance purposes.

Field parameters measured were temperature, specific conductance, and pH, using a Horiba model 24D combination meter. Calibration of the pH component was performed daily with pH 6.86 and 4.00 standards, and response was checked throughout each day. A specific conductance standard of 251 µS/cm was monitored daily. Field measurements of acidity (generally for samples with pH <7), alkalinity (generally for samples with pH >4.2), dissolved oxygen, and turbidity were performed at most water sample sites using standard field kits. When the field alkalinity measurement was <25 ppm equiva-lent CaCO3 or when the sample water was turbid, a separate sample for laboratory alkalinity determination was collected.

Filtered, acidified aliquots (FA) were collected for cation analysis by high-resolution ICP–MS. A composited sample of site water was collected in a clean 1-L polypropylene Nalgene bottle; this water was filtered on site with a 0.45-µm syringe-mounted filter into a 30-mL Nalgene bottle. The col-lection bottle, syringe, and filter were rinsed with site water; the sample bottle was rinsed with filtered site water. After collection, the FA samples were acidified to pH <2 with ultra-pure nitric acid. Unfiltered, acidified aliquots (RA) for cation analysis (as above) were collected by withdrawing water from the 1-L collection bottle with the rinsed syringe into a rinsed 30-mL sample bottle, and then acidified with ultra-pure nitric acid. Disposable gloves were worn during sample collection, clean plastic sheets were used as working surfaces at each site, and care was taken to minimize contamination.

Filtered, unacidified aliquots (FU) were collected for anion analysis by filtering (0.45-µm) water from the collec-tion bottle into a 30-mL sample bottle rinsed with filtered site water. Samples for laboratory analysis of alkalinity (ALK) were collected by filling a 125-mL bottle with unfiltered water from the collection bottle. These aliquots were not acidified but were kept cool until analyzed in the Denver, Colo., USGS laboratories.

A separate filtered, acidified aliquot (FE) was collected for the laboratory determination of ferrous and total iron. This aliquot was filtered into a brown 60-mL plastic collec-tion bottle, and acidified with ultra-pure hydrochloric acid to

Sampling Methods 5

pH <2. This subsample was collected first at each site and the collection bottle was kept from exposure to sunlight, to mini-mize photo reduction of iron (the hydrochloric acid fixes the ferrous/ferric ratio). Results from another project have shown that despite these samples being stored in plastic bottles, contamination is low and accurate analyses for dissolved organic carbon (DOC) can be obtained from the acidified iron samples (D. Fey, unpub. data), so the DOC analysis was performed on these aliquots as well.

Solid Materials

Soil

Soil samples were collected from 83 sites in 2008 (fig. 2 and plate 1). Several different samples of soil were col-lected at each site, to be processed and analyzed by different methods. Preanalysis treatments included a weak enzyme leach, sequential leach, and total digestion of the soil compo-nent. Fe complexation in soils is an important mechanism in fixing other metals. The purpose of partial leach procedures is to enhance geochemical contrasts that have developed in response to buried mineralization. Mobile elements, that is, those that are loosely bound, within the soil profile are thought to reflect vertical movement of pathfinder elements. A good review of the theory and application of partial and sequential extractions is presented in Chao (1984). With modern instru-mentation such as the quadrupole ICP–MS and high-resolution ICP–MS, extremely low concentrations (<1 μg/L) of analytes may be detected. The different extractions are more thor-oughly described in the analytical methods section, below.

In general, a pit about 0.6 m (2 ft) wide and 0.7 m (2.3 ft) deep was dug through the tundra at each site. Generally, two different soil subsamples were collected, each according to recommendations from cooperators to adhere to protocols for any given method. The three-letter codes in the bullets below match the suffixes for field names for sample media in the analytical tables.

• STO(Soil,Total)—A vertical composite sample was taken from each pit at the zone between 10 and 25 cm below the organic layer (the B horizon in most cases) and was hand sorted (gloved hands) to exclude mate-rial >2 mm. The bulk material was sieved in the USGS labs to minus-80 mesh and ground to minus-100 mesh (<0.149 mm). This fraction was submitted for the 4-acid near-total and sinter total analyses by SGS Min-erals (USGS contract lab). A total of 83 STO samples were collected for analysis.

• SCH(Soil,ColdHydroxylamine)—Bulk material was collected from the same zone as described for STO and sieved in the USGS labs to minus-80 mesh and submit-ted to ALS Chemex and analyzed using a cold hydrox-ylamine leach method. A total of 83 SCH samples were collected for analysis.

• SPH(SoilpH)—Bulk material was collected from the same zone as described above for STO (and not sieved) for analyses of soil pH and conductivity in the USGS laboratories. A total of 83 SPH samples were collected for analysis.

• SEZ(Soil,EnzymeLeach)—The sample was collected from each pit at a zone between 10 to 15 cm (4 to 6 in) below the surface for analyses by the enzyme leach method by Skyline Labs. Most commonly this was within the B horizon and the sample was designated with an SEZ suffix. However, if still within the A hori-zon at this depth, the sample was collected and labeled SEZA, and a second sample was taken about 10 cm (4 in) below the top of the B horizon (labeled SEZB). Occasionally, ice was encountered at depth and collec-tion of the SEZB sample was not possible. For each sample, the material was placed into a 50-mL plastic centrifuge tube, packed tightly with no headspace, capped, and kept cool until analyzed. A total of 107 samples were collected from 83 sites for analysis.

• STL(Soil,TerraSolLeach)—The same sample col-lected for enzyme leach analysis was also analyzed by the terrasol leach method by Skyline Labs. A total of 107 samples were collected from 83 sites for analysis.

• SIL(Soil,IonicLeach)—Bulk material was collected from the same zone as described for STO and sieved in the USGS labs to minus-80 mesh and analyzed by the Ionic Leach method by ALS Chemex. A total of 83 SIL samples were collected in 2008 for analysis, but 14 of these had insufficient sample weights; thus, analy-ses are only reported for 69 of the 83 samples. Ionic Leach is a new method introduced by ALS Chemex in 2008. For consistency with other leach methods, splits of 81 samples collected in 2007 were also submitted for analysis by Ionic Leach. Of these, four had insuf-ficient sample weights; thus, analyses are only reported for 77 of the 81 samples collected in 2007. In total, 146 samples from 2007 and 2008 have analyses by Ionic Leach reported here.

Stream Sediment

Bedload stream-sediment samples were collected at 13 sites, mostly from upper Talarik Creek and Koktuli River (fig. 2 and plate 1). An integrated composite streambed-sediment sample was collected from 10–20 sites within 15 m (50 ft) of the plotted sample locality; material was collected from the active channel alluvium. Each sample composite was sieved in the field using a 10-mesh (2 mm) stainless-steel screen. The minus-10-mesh fraction was retained and the larger size frac-tion was discarded. Samples were air dried in the laboratory, sieved to minus-80 mesh (<0.18 mm), and the minus-80-mesh fraction was ground to minus-100 mesh (<0.149 mm) before analysis.


Pond Sediment

Samples of pond bedload sediment, taken from the top 15 cm (6 in), were collected from 60 ponds within and outside of the deposit area (fig. 2 and plate 1). Samples were obtained using a PVC scoop with a 1.5 m (60 in) handle. Twenty subsamples were collected where practical to make a compos-ite. Sample material ranged from nearly total organic mat to sorted detrital gravel, sand and silt. The material was washed and screened through a 10 mesh (2 mm) stainless steel screen. Samples were air dried in the laboratory, sieved to minus-80 mesh (<0.18 mm), and the minus-80-mesh fraction was ground to minus-100 mesh (<0.149 mm) before analysis.

Pond-sediment Core

Sediment cores were collected from two ponds within the deposit area (samples 08PB255CR and 08PB256CR; fig. 2 and plate 1). Core sites were chosen based on high metal concen-trations determined for pond surface waters collected during the 2007 field season. A 10.1 cm-diameter (4 in) polycarbon-ate core barrel with an aluminum head and equipped with an anti-suction valve was pounded into the sediment with a sledge hammer until refusal. Stratification was not observed in the pond core sediments. The cores were extracted by hand, capped, and kept upright during transport to the Iliamna field facility. They were then frozen and transported to USGS labo-ratories in Denver. In the laboratory, the cores were sectioned into 2-cm (0.8 in) increments, described, air-dried, sieved to minus-80 mesh (<0.18 mm), and the minus-80-mesh fraction was ground to minus-100 mesh (<0.149 mm) before analysis. A total of 49 subsample increments (21 subsample increments for core 08PB255CR and 28 subsample increments for core 08PB256CR) were analyzed.

Analytical Methods

The following sections describe the different methods and instrumentation used to analyze various sample media. Analytical method names, in brackets, correspond to analyti-cal method names used in the accompanying Access and Excel databases.

Water

Field Parameters

Field parameters were measured and recorded at each water sample site. These included acidity, alkalinity, and dis-solved oxygen by field kit titration; pH, specific conductance, and temperature with a Horiba multimeter; and turbidity by meter. These parameters are in Excel and Access tables named H2O_FldChem.

Laboratory Analyses

Filtered, nitric-acidified (FA) and raw, nitric-acidified (RA) water samples were analyzed by high-resolution ICP–MS by Actlabs [H2O_ICPMS-HR-FA] (Actlabs Group, 2008). A list of elements and their reporting limits for the HRICP–MS water analyses are in Appendix Table 1-1.

Filtered, unacidified (FU) water samples were analyzed for the anions F–, Cl–, SO4

–2, and NO3– by ion chromatography

in USGS labs [H2O_Anions] (Theodorakos and others, 2002). Unfiltered, unacidified samples were analyzed for total alkalin-ity in USGS labs by titration [H2O_Alk] (Theodorakos, 2002). Filtered, hydrochloric-acidified samples were analyzed for ferrous/ferric iron content by a ferrozine method in USGS labs [H2O_Fe] (To and others, 1999). These same samples were also analyzed for dissolved organic carbon in USGS laborato-ries by combustion-infrared detection [H2O_DOC] (Shimadzu Corporation, 1997). A list of elements and their reporting lim-its for anions, alkalinity, dissolved organic carbon, and ferrous iron are in Appendix Table 1-2.

Solid Materials

Soil Analyses

As discussed in the above section on sample collection, the soil samples were subjected to varied analytical treat-ments. Treatments ranged from a weak, deionized water leach to a total sinter digestion. In approximate order of increasing digestion/extraction strength, a brief description of each leach procedure follows:

1. Soil pH and conductivity. This procedure was applied to an unsieved portion of the STO soil mate-rial. An extract was prepared by combining soil with water in a 1:3 ratio and stirring for five minutes. The pH and specific conductance were then measured on the slurry [Soil_pH-Cond] (Natural Resources Conservation Service, 1996, p. 415–417).

2. Enzyme leach. This is a proprietary leach designed to release weakly bound elements from soil (amor-phous manganese oxides), developed and performed by Skyline Labs on the SEZ soil subsample. The leachate analysis was by ICP–MS [Soil_ICPMS-EELch] (Skyline Assayers and Laboratories, 2009).

3. TerraSol leach. This is a proprietary leach, some-what stronger than the enzyme leach, designed to release weakly bound elements from soil (amor-phous iron oxides; for example, limonite), developed and performed by Skyline Labs on the SEZ soil subsample. The leachate analysis was by ICP–MS [Soil_ICPMS-TSLch] (Skyline Assayers and Labo-ratories, 2009).

Relational Database 7

4. Cold hydroxylamine hydrochloride (0.1 M). This leach is somewhat stronger than those previous, and is designed to release metals from manganese oxides (Chao, 1984), but very little from amorphous iron hydroxides. This leach was performed by ALS Chemex on the SCH soil subsample, and the analysis was by ICP–MS [Soil_ICPMS-CHHLch] (ALS Laboratory Group, 2008).

5. Ionic Leach. This leach is similar to the hydroxyl-amine leach in strength (depending on hydroxyl-amine concentration) but designed to release metals from the amorphous iron oxide phase, without attacking crystalline iron oxide phases. Fifty-gram aliquots of the SIL soil subsamples are subjected to a sodium cyanide solution, buffered to pH 8.5, which contains ammonium chloride, citric acid, and EDTA as chelating agents (Mary Doherty, ALS Chemex, written commun.). The analysis was by ICP–MS [Soil_ICPMS-ILch].

6. Four-acid digestion and sodium peroxide sinter. The STO soil subsamples were subjected to a mixture of hydrochloric, nitric, perchloric, and hydroflu-oric acid. This is a near-total digestion, but some refractory minerals are not completely dissolved. The solutions were analyzed by both ICP–AES and ICP–MS [Soil_ICPAES–MS42]. The subsamples were also subjected to a sodium peroxide sinter, which is essentially a “total” digestion. The result-ing solutions were also analyzed by ICP–AES and ICP–MS [Soil_ICPAES-MS55]. These digestions and analyses were performed on a contract lab basis for the USGS by SGS Minerals (SGS, 2008).

A list of elements and their respective reporting limits for soil methods 2–6 are in Appendix Tables 1-3a–1-3c.

Additional single element analyses were performed on the STO soil subsample by SGS Minerals. These were (1) antimony by hydride generation–atomic absorption spec-trometry following a sodium peroxide sinter; (2) selenium by hydride generation–atomic absorption spectrometry follow-ing a mixed-acid digestion; (3) gold by atomic absorption spectrophotometry following a fire assay preconcentration; (4) Cl- and F- by ion-specific electrode, following fusion with alkali hydroxide and nitrate; and (5) analyses for total carbon (combustion/IR detection), carbonate carbon (calculated from coulometric titration for CO2), and organic carbon (calcu-lated difference between total and carbonate carbon). These analyses are in table [Soil_AddlChem]. Reporting limits for single-element analyses of soil, stream sediment, pond sedi-ment, and pond-sediment core samples from SGS Minerals are in Appendix Table 1-3c.

Stream Sediment Analyses

The stream-sediment samples (suffix “STS”) were digested and analyzed in the same manner as method 6 for the soil samples [StreamSed_ICPAES–MS42 and StreamSed_ICPAES-MS55]. Reporting limits are in Appendix Table 1-3c. They were also analyzed for five additional elements (Sb, Se, Au, Cl-, F-), and forms of carbon as described above. In addi-tion, the stream-sediment samples were analyzed for Hg by flow-injection cold-vapor atomic absorption following a mixed acid-digestion [StreamSed_AddlChem].

Pond Surface and Core Sediment Analyses

The pond-sediment samples (suffix “PDS”) and pond core samples (suffix “CR”) were digested and analyzed in the same manner as method 6 for the soil samples [PondSed_ICPAES–MS42 and PondSed_ICPAES-MS55] and [PondSed-Core_ICPAES–MS42 and PondSedCore_ICPAES-MS55]. Reporting limits are in table Appendix 1-3c. They were also analyzed for five additional elements (Sb, Se, Au, Cl-, F-), and forms of carbon as described above. In addition, the pondcore subsamples were analyzed for Hg by flow-injection cold-vapor atomic absorption following a mixed acid-digestion [PondSed_AddlChem] and [PondSedCore_AddlChem].

Relational Database

Because of the scope and complexity of data collected as part of the Pebble deposit study, a relational database structure was designed for data storage. The Pebble deposit relational database was constructed for use as a data synthesis and analy-sis tool and as an archive of data collected during the study. It includes data from samples collected by USGS geoscientists within and adjacent to the Pebble deposit during the sum-mer of 2008, as well as data from samples collected during the summer of 2007 that were not included in Fey and others (2008). The database structure is very similar to that used for 2007 Pebble sample results that were published by Fey and others (2008) and contains field measurements and labora-tory analyses of samples collected at point locations. Quality assurance/quality control descriptions and interpretations are included in this report (see Data Quality Control and Quality Assessment section) but are not present in the database itself, nor in the accompanying tables that have been derived from the database.


Contents of Database

The Pebble deposit database (USGSPebbleDeposit2.mdb) contains seven relational datasets. These datasets comprise all of the data derived from samples collected during 2008, and all of the data discussed in this report. The database also contains Au data on 2007 STO soil samples that were reanalyzed for Au, and new ionic leach data on 2007 SIL soil samples. The 7 datasets, representing various types of data, were organized into 24 analytical data tables (fig. 3). A table of field name definitions was also created [FieldNameDiction-ary]. Data were collected at 237 sites (plus 13 duplicates) (fig. 2 and plate 1). The database includes 71,548 results for 562 water subsamples, 691 soil subsamples, 60 pond-sediment grab samples, 49 pond-sediment core samples and 13 stream-sediment samples. These entries contain quantitative,

qualitative, and descriptive measurements. Data type descrim-ination is provided through the use of 229 unique parameters, or measurement types.

Database Structure

Data are grouped into seven primary logical units (tables), 24 secondary derivative tables, and relationships are defined to link the tables. This structure provides effi-cient storage of information, and provides for built-in data verification checks. For example, all valid results must have corresponding site, sample, and parameter information. The relational database structure is useful for efficient retrieval of subsets of data to meet user requirements.

The seven principal tables in the database are the FieldSite, Sample, QuantResult, QualResult, Parameter,

Figure 3. Tables in the relational database and the relationships between tables.1

1The symbols “1” and “∞” at the ends of the relationship line indicate a one-to-many relationship; for example, a single site may have many samples

Relational Database 9

AnalyticMethod, and LabName tables (fig. 3, table 1). The FieldSite table contains information about each of the 237 sample sites in the database. FieldSiteNumber is the key field that uniquely identifies each site, which may be further described with data entered in the SiteLocationInfo, SiteDesc, and SiteComment fields. FieldSiteNumber is also the linking field between site and sample in a one-to-many relationship. The FieldSite table also includes GPS geographic coordinate information in decimal degrees and in degrees/minutes/sec-onds (FieldLatitude_DD, FieldLongitude_DD, FieldLatitude_DMS and FieldLongitude_DMS), geologic and mineral deposit information, and information regarding weather conditions at the time of sampling. The relationship between the FieldSite table and other tables in the database is shown in figure 3.

The Sample table contains information about the sample material collected at each site. Each analyzed sample has a unique SampleID, as well as a SampleNumber that was pro-vided by the sample collector. SampleID is the key field that links the sample to its chemical and physical data found in the QuantResult and QualResult tables. SampleID also links the sample to data found in the 24 derivative tables. The time and date of sample collection are noted in the SampleTime and SampleDate fields. The field SampleMediaGross defines the sample material type, while SampleMediaDetail and Sample-Desc provide more detailed information about the sample. Media type should be carefully noted when assessing data so that data from different sample types are not mistakenly equated. For example, the database contains analyses for cop-per found in five different subsamples that were derived from one soil sample site. The data in SampleMediaDetail show the different types of sample treatment used in preparation for dif-ferent analytical methods that detect differing concentrations of copper. Information regarding the collection and prepara-tion of the sample may be found in the optional fields Collec-tionMethod, FieldSamplePrep, LabSamplePrep, and SieveSize. The LAB_ID and JOB_ID information created by the various analytical laboratories, though not required, is found in the Sample table. Relationships between the Sample table and other tables in the database are shown in figure 3.

The QuantResult table contains laboratory and field measurements, expressed as numeric values, whereas the QualResult table (fig. 3) contains qualitative measurements that are expressed as text values. For the most part, the two tables function in the same way. Most of the project geochem-ical data are found in the QuantResult table. The measured characteristic is identified using a ParameterCode that can be used as a column name in a data report or spreadsheet. The ParameterCode links both result tables to the Parameter look-up table, which is further detailed later in this section. In the QuantResult table, measurements consist of a numeric QuantValue and an optional QuantValueQual, which is used to qualify results such as nondetects or estimates based on limits of instrumental detection. Information regarding the method of analysis or measurement used to obtain data is found in the AnalyticMethodShortName field, an abbreviated label linked to the AnalyticMethod look-up table, and provides additional

information on field and laboratory techniques used for sample analysis. Likewise, LabShortName is an abbreviated label linked to the LabName look-up table and provides informa-tion regarding the laboratory or work group responsible for the analysis. Any further remarks regarding the Value or the analytic process are found in the QuantValueComment field. Relationships between the QuantResult and QualResult tables and other tables in the database are shown in figure 3.

The Parameter table is a look-up table that contains a complete description of each characteristic measured. Whereas the QuantResult table contains a short description of the characteristic measured (ParameterCode), due to the highly specific nature of laboratory measurements, a lengthier description is needed. For example, the ParameterCode “Cu_ug/L” is shorthand for “Copper, laboratory, micrograms per liter.” The Parameter table also includes a ConstituentName field to group results according to the element or compound (Zn or SO4

–2, for example), and a ReportUnitsfield that shows the units in which values are reported.

Relationships between these tables are depicted as lines in figure 3. The FieldSite table is linked to the Sample table by including a common field (FieldSiteNumber) in both tables. Therefore, a sample cannot exist without having a site in the FieldSite table. The symbols “1” and “¥” at the ends of the relationship line indicate a one-to-many relationship; for example, a single site may have many samples. Similarly, a sample may have many results, and a parameter may also have many results. Data may be extracted from the Pebble deposit relational database to meet specific user needs by constructing user-defined queries.

To facilitate ease of use, each of the 24 tables represents a unique dataset containing analytical data gathered from a specific sample media by way of a certain analytic method (media/method specific datasets). For example, the table H2O_ICPMS-HR-FA contains chemical concentrations in filtered, acidified water obtained by high resolution inductively coupled plasma–mass spectrometry (ICP–MS). To further aid the user, these tables were used to create spreadsheets of all the information in the database. The table FieldNameD-ictionary contains the field name, definition, and general data type of the 523 fields that are used in the tables of the Pebble deposit relational database, as well as the table or tables in which these fields appear. This is of particular importance as it also contains the field names of the 24 cross-tab chemical data tables. These tables have also been exported as Excel spreadsheets and as tab-delimited text files for use by the non-database user and are attached to this report in the fold-ers “Pebble Deposit Spreadsheets” and “Pebble Deposit Text Files”. A summary of the Excel file names and a brief descrip-tion of contents are in table 1.

Relational databases can be implemented using a vari-ety of proprietary or non-proprietary software packages. The Pebble deposit relational database is attached to this report in a proprietary (Microsoft Office Access 2003) and non-proprietary (ASCII tab-delimited) format. The spreadsheets are accessible in the same manner in Microsoft Office Excel 2003 format.


Table 1. List of Pebble deposit spreadsheets.

Spreadsheet name Spreadsheet descriptionAnalyticMethod.xls Analytical method criteriaFieldNameDictionary.xls Field name dictionaryFieldSite.xls Field site criteriaLabName.xls Laboratory nameSample.xls Sample criteria

H2O_Alk.xls Alkalinity of filtered, unacidified waterH2O_Anions.xls Anions in filtered, unacidified waterH2O_DOC.xls Dissolved organic carbon in filtered, acidified waterH2O_Fe.xls Ferrous, ferric and total iron in filtered, acidified waterH2O_FldChem.xls Field chemistry parameters of waterH2O_ICPMS-HR-FA.xls Cations in filtered, acidified water by high-resolution ICP–MSH2O_ICPMS-HR-RA.xls Cations in unfiltered, acidified water by high-resolution ICP–MS

PondSed_AddlChem.xls Constituents in pond sediment by AA, ISE, titration, combustion and fire assayPondSed_ICPAES-MS42.xls Cations in pond sediment by ICP–AES and ICP–MS after 4-acid digestionPondSed_ICPAES-MS55.xls Cations in pond sediment by ICP–AES and ICP–MS after sinter digestion

PondSedCore_AddlChem.xls Constituents in pond sediment by AA, ISE, titration, combustion and fire assayPondSedCore_ICPAES-MS42.xls Cations in pond sediment core by ICP–AES and ICP–MS after 4-acid digestionPondSedCore_ICPAES-MS55.xls Cations in pond sediment core by ICP–AES and ICP–MS after sinter digestion

StreamSed_AddlChem.xls Constituents in stream sediment by AA, ISE, titration, combustion and fire assayStreamSed_ICPAES-MS42.xls Cations in stream sediment by ICP–AES and ICP–MS after 4-acid digestionStreamSed_ICPAES-MS55.xls Cations in stream sediment by ICP–AES and ICP–MS after sinter digestion

Soil_AddlChem.xls Constituents in soil by AA, ISE, titration, combustion and fire assaySoil_ICPAES-MS42.xls Cations in soil by ICP–AES and ICP–MS after 4-acid digestionSoil_ICPAES-MS55.xls Cations in soil by ICP–AES and ICP–MS after sinter digestionSoil_ICPMS-CHHLch.xls Constituents in soil by ICP–MS after cold hydroxylamine hydrochloride leachSoil_ICPMS-EELch.xls Constituents in soil by ICP–MS after enhanced enzyme leachSoil_ICPMS-ILch.xls Constituents in soil by ICP–MS after ionic leachSoil_ICPMS-TSLch.xls Constituents in soil by ICP–MS after TerraSol leachSoil_pH-Cond.xls pH and specific conductance of soil/de-ionized H2O paste

Data Quality Control and Quality Assessment 11

Data Quality Control and Quality Assessment

Sources of Geochemical Variation and Methods for Assuring Data Quality

There are several sources and levels of variation in geo-chemical data—for instance, between-site variation, site varia-tion, sample inhomogeneity, and analytical variation. Statistical analysis of variation (ANOVA) sampling design generally shows that the primary variation in geochemical data is that found between individual samples at different and widely spaced sites (between-site variation). This variation is due to differences in sample parent material, local geology, mineralization processes, and possible anthropogenic influences. This variation provides areal geochemical contrasts that help delineate geochemical anomalies in exploration programs. The goal of regional geo-chemical surveys is to discern and interpret “between-site varia-tion” by reducing other sources of geochemical variation.

The next level of geochemical variation is known as “site variation”. Soils, sediments, and rocks are usually heteroge-neous at any location; a single grab sample from one spot at a sample site may have different element concentrations from another grab sample collected a few meters away. This varia-tion can be reduced by compositing several subsamples within the immediate area of sample collection, resulting in a more representative sample of the entire site. Usually a certain fraction (commonly between 10 and 20 percent) of sites is sampled twice. These “site duplicates” are then used to assess the efficacy of the sampling design at reducing site variation. Differences between sampling methods, sampling equipment, and individual collectors can also introduce variation as well as contamination. This variation can be reduced by establish-ing rigorous sampling protocols, providing identical sets of sampling equipment, and conducting training programs.

Variation is also found within any single sample due to inherent heterogeneity. Sample heterogeneity can be reduced by establishing a consistent sample preparation protocol. A process of crushing, grinding, mixing, and splitting the sample typically creates a very fine homogenous powder from the original heterogeneous material. Despite consistent prepara-tion procedures, some sample inhomogeneity may not be totally eliminated. For example, samples with small grains of native gold are notoriously difficult to process. The malleable nature of native gold resists the efforts of crushing and grind-ing. In addition, inhomogeneous distribution of gold particles in the processed sample (due to settling or incomplete mix-ing) can cause variability in the analyses. This is known as the “nugget effect”. If the analyst happens to get a “nugget” of gold in the material that is analyzed, the results will show a high concentration of gold. On the other hand, a second analysis of the same sample may miss the “nugget” and, despite the presence of gold in the sample, give low results for gold. Larger sample aliquots and attention to fine grinding help to reduce this error for gold and similar elements.

Laboratory analytical procedures also can be sources of variation in the geochemical data. These sources include dif-ferences in analysts, dissolution procedures, analytical instru-ments, instrument calibration errors, and instrument drift. The combined variation due to sample preparation, aliquot size, and analytical procedures (commonly called “analytical varia-tion”) can be measured by using standard reference materials, analytical duplicates, and blanks.

Quality Assurance/Quality Control Methods

A quality management system for a standard geochemi-cal survey includes both quality assurance (QA) and quality control (QC) elements. The QA focus is mainly in the ana-lytical laboratory environment. Under the QA umbrella, the components of standard operating procedures, instrument logs, training records, data acceptance/rejection criteria, and lab audits are covered. The QA element is not easily measured. However, the QC element provides measures of the accuracy and precision of geochemical data produced by an analytical method. The accuracy and precision are established through the analysis of standard reference materials (SRMs), analytical duplicates, and blanks.

The precision of an analytical method is measured by the percent relative standard deviation (percent RSD) of data for a number of runs of a particular sample or standard and is calcu-lated by dividing the standard deviation (SD) by the mean and multiplying by 100. The SD is defined as the square root of the quantity {sum of squares of deviations of individual results from the mean, divided by one less than the number of results in the set} (Dux, 1986):

The precision of an analytical method can also be deter-mined from the assessment of analytical duplicates: samples that were split before analysis and then analyzed as two sepa-rate samples. The percent RSD is again calculated by dividing the standard deviation (SD) by the mean and multiplying by 100. However, the standard deviation for duplicate measure-ments is defined as the square root of the quantity (sum of squares of the difference between the duplicate results (R), divided by two times the number of sets of duplicate samples) (Dux, 1986):

The accuracy of an analytical method is measured by the percent recovery, which is calculated by dividing the mean concentration by the target value of the standard reference material used and multiplying by 100. Target values for standard reference materials may consist of certified values or, when certified values are not available, informational values. The percent recovery derived from informational values is not

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as reliable as the percent recovery calculated from certified values. In general, most selective leach methods do not have certified standard reference material values. Unless otherwise stated, it is expected that most of the SRM target values pro-vided by the individual laboratories for their leach methods are informational values.

Measurements of precision and accuracy are best when elemental concentrations fall within the middle of the determination range for a specified analytical method and element. As a general rule, analytical determinations become less accurate and precise as data values approach the lower or upper reporting limits. For this report, percent RSD and percent recovery values are given more weight when they are calculated on mean values greater than five times the lower reporting limit.

Possible contamination during the analytical procedure is assessed through the use of “procedure blanks.” Blanks are defined based on the sample medium and analytical method and are processed concurrently with samples to determine whether contamination has occurred during the sample dis-solution stages or whether cross-sample contamination has occurred in the analytical instrument during a sample run. Commonly, blanks are a set of all the reagents used in the sample processing and analysis procedure.

Quality Control Samples

Each of the analytical laboratories commonly analyzes a small number of SRMs with every batch of samples. It is also a common practice for most laboratories to pick a small percentage of submitted samples in a batch and analyze them a second time as an analytical duplicate. When appropriate, blank samples are also inserted into the batch by the labora-tory. In this study, the data for these quality control samples were requested from each laboratory so that the analytical variation in each data set could be assessed.

For most of the laboratories, the USGS submitted addi-tional quality control samples within each batch of samples sent. These included sample splits for analytical duplicates and a suite of USGS-prepared standard reference materi-als (SAR–L, SAR–M, DGPM, and GSP–QC). Two Pebble project soil standards were also submitted for analysis. These two standards were created by compositing and homogeniz-ing excess minus-80 mesh material derived from processing all of the soil samples from the 2007 field season: a B-horizon mineral soil standard (PB–SMM) and an organic-rich A-hori-zon soil standard (PB–SNP). Project standards can be used to currently evaluate analytical precision in sample batches and to assess variability among samples collected and ana-lyzed for the project in the future. The advantage of a project standard over well established SRMs is that project materials have exactly the same sample matrix as the submitted samples and may reveal analytical problems unique to this project that would be missed when using SRMs prepared from other soils or other media. No target values were previously determined for the Pebble project soil standards.

Evaluation of Data Sets by Analytical Laboratory

Each of the analytical data sets were evaluated here based on the analyzed quality control samples that were reported by the laboratory. For each data set, summary quality control statistics were calculated and compiled in a series of tables. Where appropriate, quality control charts for data precision (percent RSD) and data accuracy (percent recovery) were also created. These tables and charts, organized by data set, are shown in appendices 2–8.

Quality control charts based on percent RSD and percent recovery statistics are a tool to help to quickly focus on ele-ments that may be a problem in a dataset. However, because several factors can strongly influence these statistics, decisions concerning the validity or applicability of the data should not be made solely on the results of these charts. Some factors that are beyond the control of the laboratory include single data outliers, samples with anomalously high or low concentrations, and a lack of homogeneity in the chosen analytical duplicate samples or reference material (the “nugget effect”). Another factor that influences these statistics is the use of very small quality control data sets composed of only two or three analy-ses. Often just a review of the actual quality control data for an element identified from the quality control charts will show that the variation is still within an acceptable range for the purposes of the data. In rare cases, it may be necessary to contact the responsible laboratory to resolve an issue with the data.

Each of the following sections summarizes the analytical results determined by evaluating the quality control tables of statistics and charts. For most methods, the precision charts include a line showing a conservative “Control Limit” of 15 percent RSD. The accuracy charts include lines at 85 percent recovery and 115 percent recovery. These lines are used to identify elements that might be problematic and to guide the following discussions.

It should be noted that the ±15 percent guidelines were developed to assess the performance of near- and total-diges-tion techniques, like 4-acid, sinter, and fusion methods. Vari-ability in instrumental performance, analyzing solutions with analytes at greater than 10 times instrumental detection limits, is usually at the five percent level. Thus, the variation seen in the following techniques is predominantly a result of sample or digestion/extraction variability.

Even near-total digestions such as the 4-acid techniques typically do not liberate the total mass of “refractory” ele-ments such as Sn, Ti, Cr, or rare earths. Percent recovery and precision values for these elements are less than for more easily-solubilized elements. The variability in recovery and precision for partial extraction techniques for the above and other elements is usually much higher than for more complete digestions. The partial techniques typically release only small percentages (sometimes less than one percent) of the mass of a given sample, so the variability is higher. Percent relative standard deviation (RSD) values as high as 50 percent are not unusual, nor are they grounds for dismissal of a technique or an element.


It is important to keep in mind that the purpose of applying partial-leach techniques is to develop geochemical data–generally grouped into classes–that describe geochemical contrasts. The class boundaries may cover several orders of magnitude concentration, and so individual element variation on the order of 50 percent will not significantly change the interpretations.

Skyline Assayers and Laboratories Enzyme Leach of Soils

Two batches of soil samples were sent to Skyline Labs to be analyzed using their proprietary Enzyme Leach method. The first set of samples was collected in July of 2008 and the second set was collected later in September. Skyline Labs inserted twelve quality control samples into those two batches of soil samples: six samples of their laboratory reference mate-rial QAlqt and six samples of their laboratory reference mate-rial QRd. Four more quality control samples were submitted by the USGS: two samples of the Pebble project reference material PB–SMM and two samples of the Pebble project ref-erence material PB–SNP. In addition, Skyline Labs selected fourteen of the submitted soil samples (the first, the last, and every tenth sample in each batch) to be analyzed as analytical duplicates. The results for analytical blanks were not included in the Skyline Labs QC reports.

Appendix 2 contains three tables of summary statis-tics for the Skyline Labs quality control samples: analytical duplicates (table 2-1), laboratory SRM QAlqt (table 2-2), and laboratory SRM QRd (table 2-3). These results are also repre-sented in five quality control charts: precision (percent RSD) of analytical duplicates (fig. 2-1), precision of SRM QAlqt (fig. 2-2), accuracy (percent recovery) of SRM QAlqt (fig. 2-3), precision of SRM QRd (fig. 2-4), and accuracy of SRM QRd (fig. 2-5). The QC results returned for Enzyme Leach analysis of Pebble project SRMs are not included here due to the small number (n = 2 for each standard) of samples.

Skyline Labs differentiates element analyses in their enzyme leach method as either quantitative or semiquanti-tative. Even so, the precision graphs for analytical SRMs QAlqt (n = 6; fig. 2-2) and QRd (n = 6; fig. 2-4) show excel-lent results with only a few elements exceeding 15 percent RSD and none above 25 percent RSD for either SRM. The graph for precision (percent RSD) of analytical duplicates also shows generally good results for the 14 duplicate pairs (fig. 2-1). Most elements are below 30 percent RSD; the only ones that exceed that are As at 34 percent, Cl at 31 percent, Mo at 42 percent, Pb at 76 percent, and Ta at 62 percent. These ana-lytical duplicate results are very similar to those reported for the Enzyme Leach analysis of Pebble soils in 2007 (Fey and others, 2008) and suggests that the Pebble project soils are less homogeneous than either the QAlqt or QRd SRMs.

The accuracy (percent recovery) graph for QAlqt (fig. 2-3) shows a strong systematic exceedance of the 115 percent control limit. Forty-one elements exceed the limit, ranging between 115 and 185 percent. Mercury has been removed

from the graph due to a value of 650 percent. Only 17 ele-ments fall within the control limits. Three elements (Au, Cr, and Pb) fall below the 85 percent limit, with Cr being the low-est of these at 31 percent. This same standard was assessed for soil samples analyzed from the USGS 2007 field season, and results from those analyses showed fewer and lower exceedances (Fey and others, 2008). Although the reasons for the differences between 2007 and 2008 analyses are unclear, Skyline Laboratories states that with the exception of Hg, concentrations for all other elements in the QAlqt standard were within their normal ranges (Skyline Laboratories, 2009, written commun.).

The accuracy graph for QRd (fig. 2-5) shows better per-formance by most elements. Beryllium, Cl, I, Mo, S, and Se exceed the 115 percent control limit, with Cl at 142 percent, Mo at 130 percent, and Hg at 410 percent, with the rest below 125 percent. Similar to QAlqt, Au and Cr, with the addition of K, fall below the 85 percent lower control limit; the lowest of these is Cr at 23 percent.

Skyline Assayers and Laboratories TerraSol Leach of Soils

The soil samples submitted to Skyline Labs for Enzyme Leach determinations were also used for a proprietary Terra-Sol Leach analysis. Skyline Labs inserted twelve quality control samples into the analytical batches: six samples of their laboratory analytical reference material QAlqt and six samples of their laboratory analytical reference material QRd. Four quality control samples were submitted by the USGS: two samples of the Pebble project analytical reference material PB–SMM, and two samples of the Pebble project analytical reference material PB–SNP. Fourteen analytical duplicates were selected by Skyline Labs from the batch of soil samples. The results for analytical blanks were not included in the Sky-line Labs QC reports.

Appendix 3 contains four tables of summary statistics for the Skyline Labs quality control samples: analytical duplicate pairs (table 3-1), laboratory SRM QAlqt (table 3-2), labora-tory SRM QRd (table 3-3), and Pebble project SRM PB–SNP (table 3-4). These results are also represented in four quality control charts: precision (percent RSD) of analytical dupli-cates (fig. 3-1), precision of SRM QAlqt (fig. 3-2), precision of SRM QRd (fig. 3-3) and precision of Pebble project SRM PB–SNP (fig. 3-4). The results for Pebble project SRM PB–SMM are not included in this report due to the small number of analyses. The results for Pebble project SRM PB–SNP are included because one sample was analyzed as a labora-tory duplicate, giving three results for the sample and thereby improving statistical analysis of the performance. Due to the TerraSol Leach being a new method, there are no expected values; as a result there are no data to analyze for accuracy.

The quality control charts for TerraSol Leach of soils by Skyline Labs show good, well-constrained results. The precision graph for analytical duplicates (fig. 3-1) shows good results for the duplicate pairs. Most are below 20 percent


RSD. Elements that exceed this are Be at 34 percent, Fe at 22 percent, Hg at 71 percent, Mn at 36 percent, U at 35 percent, V at 53 percent and Zn at 42 percent. Of these, Fe and Hg are considered semiquantitative by Skyline Labs. For Be, U, and V, one pair of samples had values with large disparities; when this pair is removed from the dataset, the percent RSDs for these elements fall below 20 percent. The precision graphs for QAlqt (fig. 3-2), and QRD (fig. 3-3), however, show excellent results. Nearly all element values are near or below 10 percent RSD in QAlqt, and near or below 5 percent RSD in QRd: The one exception is the results for the semiquantitative analysis of Hg, which exceeds 20 percent in both graphs. The precision graph for the Pebble project standard PB–SNP (fig. 3-4) also shows good results, though not as tightly constrained as QAlqt or QRd; all elements are below 15 percent with the exception of Hg at 90 percent (which has been removed from the graph for clarity), and Cu at 26, percent which is due to one anoma-lously high measurement.

ALS Chemex Cold Hydroxylamine Hydrochloride Leach of Soils

Eight quality control samples were inserted by ALS Chemex into the batch of soil samples analyzed by their cold hydroxylamine hydrochloride soil leach method: one sample of laboratory reference material LK3-ALG, two samples of labora-tory reference material LK4–ALG and five analytical duplicates chosen by ALS Chemex Labs from submitted soil samples. Ten additional quality control samples were submitted by the USGS: two samples of USGS standard reference material SAR–L, and eight samples of Pebble project standard PB–SMM.

Appendix 4 contains three tables of summary statistics for quality control samples analyzed by the ALS Chemex cold hydroxylamine hydrochloride leach method: analyti-cal duplicates (table 4-1), laboratory SRM LK4–ALG (table 4-2), and Pebble SRM PB–SMM (table 4-3). These results are also represented in five quality control charts: precision (percent RSD) of analytical duplicates (fig. 4-1), precision of laboratory SRM LK4–ALG (fig. 4-2), accuracy (percent recovery) of laboratory SRM LK4–ALG (fig. 4-3), precision of Pebble SRM PB–SMM (fig. 4-4), and accuracy of Pebble SRM PB–SMM (fig. 4-5). The means from the 2007 analyses of Pebble project SRM PB–SMM (Fey and others, 2008) were used as target values for the 2008 analyses of PB–SMM. The results returned for laboratory SRMs LK3-ALG and USGS SRM SAR–L are not reported here due to the small number of samples analyzed.

The analytical precision charts for the SRM LK4–ALG (fig. 4-2) and SRM PB–SMM (fig. 4-4) show excellent results. The precision results for the five analytical duplicate pairs (fig. 4-1) show more variation that may be due to slight inhomo-geneity of the sample material or slight variations in sample digestion. The accuracy of analyses of Pebble project SRM PB–SMM is generally quite good compared to the mean con-centrations of the 2007 analyses. No problems were noted for the accuracy results for SRM LK4–ALG (fig. 4-3).

ALS Chemex Ionic Leach of Soils

Seven samples of laboratory reference material ION–SRM18 were inserted by ALS Chemex into the soil samples analyzed by their Ionic Leach method. Eighteen additional quality control samples were submitted by the USGS: four samples of USGS standard reference material SAR–L and fourteen samples of Pebble project standard PB–SMM. Thir-teen analytical duplicates were selected by ALS Chemex for analysis from soil samples, however only one had sufficient material to create pairs and so no results were evaluated.

Appendix 5 contains three tables of summary statistics for quality control samples analyzed by the ALS Chemex Ionic Leach method: Laboratory SRM ION–SRM18 (table 5-1), USGS SRM SAR–L (table 5-2), and Pebble project SRM PB–SMM (table 5-3). These results are also represented in four quality control charts: precision (percent RSD) of labora-tory SRM ION–SRM18 (fig. 5-1), accuracy (percent recovery) of laboratory SRM ION–SRM18 (fig. 5-2), precision of USGS SRM SAR–L (fig. 5-3), and precision of Pebble project SRM PB–SMM (fig. 5-4). Blanks are not included in this report; most results were near, at, or below the reporting limit, except for three values slightly above the reporting limit for Ti.

The laboratory SRM ION–SRM18 data table (table 5-1) and quality control charts (figs. 5-1 and 5-2) show excellent results for elements with values having a mean greater than 5 times the RL. The chart for data precision (fig. 5-1) shows the only element that exceeds the 15 percent RSD control limit is Cr at 21 percent. The chart for data accuracy (fig. 5-2) shows all elements within the 85–115 percent recovery control limits except for Ti at 79 percent.

The Ionic Leach method was not available for the 2007 samples when they were initially collected and analyzed. However, splits of archived 2007 soil samples were included with the 2008 samples. Both the 2007 and 2008 samples were analyzed and the data are presented in the present report. Due to the fact that Ionic Leach is a recently developed analytical method, target values are not available and so accuracy charts could not be prepared. The data quality table (table 5-2) and precision chart (fig. 5-3) for USGS SRM SAR–L show that roughly half of the elements are above 15 percent RSD. Of these, the highest value is Pd at 81 percent.

The data quality table (table 5-3) and precision chart (fig. 5-4) for Pebble SRM PB–SMM show that most elements with values with a mean greater than 5 times the RL exceed 15 percent RSD, and all but two elements (Rb and Tb) are above 10 percent RSD. The highest values are Cr at 49 percent, Ce at 44 percent, Mo at 41 percent, and Ag at 41 percent.

SGS Minerals Services (USGS Contract) Analysis of Soils, Sediments, and Pond-sediment Cores

Soil, stream sediment, pond sediment, and pond core sediment samples were submitted to SGS Minerals, using a current USGS analytical chemistry contract, for analysis by the ICPAES–MS42 multielement package (4-acid digestion),


the ICPAES–MS55 multielement package (sinter diges-tion), and for a suite of single-element methods. Within each subbatch of samples submitted, the USGS Quality Control Manager inserted selected standard reference materials. A total of 22 SRMs were included in the soil samples submit-ted to SGS Minerals: three samples of the USGS standard reference material DGPM, four samples of the USGS standard reference material GSP–QC, seven samples of the USGS standard reference material SAR–L, and eight samples of the USGS standard reference material SAR–M. As part of this project, the USGS also submitted 20 samples of the Pebble project standard reference material PB–SMM. Up to eleven analytical duplicate pairs were selected for analysis from the soil samples, though not all pairs were analyzed or returned useable data for a particular method or element. SGS Miner-als also inserted their own SRMs and analytical blanks into the batches of submitted samples but these quality control data were not available for this assessment.

Appendix 6 contains eighteen tables of summary statis-tics for the quality control samples. An additional table (table 2) is presented to summarize the tables and figures relating to QC statistics for ICPAES–MS42, ICPAES–MS55, and single-element methods applied to the solid-material samples. This table summarizes the material in the following paragraph.

ICPAES–MS42

The ICPAES–MS42 technique is a near-total digestion followed by analysis by ICP–AES and ICP–MS. The target control limits of 15 percent RSD and ± 15 percent accuracy are more instructive here than for the previous partial-diges-tion techniques. Mean values from the 2007 analyses of the reference material PB–SMM (Fey and others, 2008) were used as target values for the assessment of analytical accuracy for 2008 PB–SMM. The data tables (tables 6-1, 6-4, 6-7, 6-10, 6-13 and 6-16) and precision quality control charts for the ICPAES–MS42 method (figs. 6-1, 6-4, 6-10, 6-16, 6-22, and 6-28) show very good results. Analytical duplicates (table 6-1, fig. 6-1) show excellent results with all elements below 15 percent RSD. Only one element consistently exceeds the 15 percent RSD control limit on any of the precision charts for ICPAES–MS42: Be on SAR–L (fig. 6-4), SAR–M (fig. 6-10), DGPM (fig. 6-16), and PB–SMM (fig. 6-28). The reference material SAR–L (fig. 6-4) shows an additional exceedance by Sn, SAR–M (fig. 6-10) shows an exceedance by Nb, DGPM (fig. 6-16) shows several exceedances by Cr, Cu, and Pb, and PB–SMM (fig. 6-28) shows one additional exceedance by W. The reference material GSP–QC (fig. 6-22) shows all values below the 15 percent RSD control limit.

Table 2. Summary of tables and charts in appendix 6, describing Quality Control sample type, analytical method, table numbers, and precision and accuracy chart numbers for solid samples analyzed by contract lab SGS Minerals for Pebble Project samples, 2008.

QC Sample Method Table of Statistics Precision Chart Accuracy ChartAnalytical duplicates ICPAES–MS42 Table 6-1 Figure 6-1 naAnalytical duplicates ICPAES–MS55 Table 6-2 Figure 6-2 naAnalytical duplicates Various methods Table 6-3 Figure 6-3 naSAR–L ICPAES–MS42 Table 6-4 Figure 6-4 Figure 6-5SAR–L ICPAES–MS55 Table 6-5 Figure 6-6 Figure 6-7SAR–L Various methods Table 6-6 Figure 6-8 Figure 6-9SAR–M ICPAES–MS42 Table 6-7 Figure 6-10 Figure 6-11SAR–M ICPAES–MS55 Table 6-8 Figure 6-12 Figure 6-13SAR–M Various methods Table 6-9 Figure 6-14 Figure 6-15DGPM ICPAES–MS42 Table 6-10 Figure 6-16 Figure 6-17DGPM ICPAES–MS55 Table 6-11 Figure 6-18 Figure 6-19DGPM Various methods Table 6-12 Figure 6-20 Figure 6-21GSP–QC ICPAES–MS42 Table 6-13 Figure 6-22 Figure 6-23GSP–QC ICPAES–MS55 Table 6-14 Figure 6-24 Figure 6-25GSP–QC Various methods Table 6-15 Figure 6-26 Figure 6-27PB–SMM ICPAES–MS42 Table 6-16 Figure 6-28 Figure 6-29PB–SMM ICPAES–MS55 Table 6-17 Figure 6-30 Figure 6-31PB–SMM Various methods Table 6-18 Figure 6-32 Figure 6-33


The data accuracy quality control charts for the ICPAES–MS42 method (figs. 6-5, 6-11, 6-17, 6-23, and 6-29) show nearly the same quality results: Be exceeds the 115 percent control limit on SAR–L (fig. 6-5), DGPM (fig. 6-17), and GSP–QC (fig. 6-23). Bi exceeds this limit on SAR–M (fig. 6-11) and PB–SMM (fig. 6-29). Other upper control limit exceedances are Sb and Te on SAR–M (fig. 6-11), and Pb on DGPM (fig. 6-17). Lower control limit exceedances include P and Sn on SAR–L (fig. 6-5), Ni on GSP–QC (fig. 6-23), and S and Zn on PB–SMM (fig. 6-29). Lower control limit exceedances for SAR–M are for the elements P, Sn, Ti, U, W and Y (fig. 6-11). The farthest outlier on this chart is for Sn, at 31 percent. An examination of the data shows that the mean value was 2.94 ppm in the samples, while the target value was 9.4 ppm. This low recovery is typical of Sn for a mixed-acid digestion; fusion and sinter techniques are required to fully dissolve several mineral phases containing Sn, even at low levels.

Analytical results for Be tend to show more variability in a variety of materials. The concentrations display a nar-row range of about 0.1 to 2 ppm. The variance in results is probably due more to sample heterogeneity than analytical uncertainty.

ICPAES-MS55

The ICPAES–MS55 technique is a sodium peroxide sinter decomposition followed by analysis by ICP–AES and ICP–MS. The target control limits of 15 percent RSD and ± 15 percent accuracy are more instructive here than for the previous partial-digestion techniques. Mean values from the 2007 analyses of the project reference material PB–SMM (Fey and others, 2008) were used as Target Values for the assessment of analytical accuracy for 2008 PB–SMM. The data tables (tables 6-2, 6-5, 6-8, 6-11, 6-14, and 6-17) and precision quality control charts for the ICPAES–MS55 method (figs. 6-2, 6-6, 6-12, 6-18, 6-24, and 6-30) show very good results.

Lithium consistently exceeds the 15 percent RSD control limit for all of the standard reference materials analyzed by the ICPAES–MS55 technique. This contrasts with the low analytical variability for Li in the ICPAES–MS42 digestion, and suggests that the sodium peroxide sinter digestion matrix affects the instrumental precision for Li. Indeed, the reporting limit for Li by the sinter method is 10 ppm, 10 times higher than for the acid digestion method. This puts the Li results into range of values having a mean less than 5 times the RL, and so the exceedance is acceptable.

The precision and accuracy charts show that Ni consis-tently is out of control for the ICPAES–MS55 technique. For example, the reported concentration for Ni in both GSP–QC and DGPM ranged from below the reporting limit of 5 ppm to over 70 ppm, when their target values are 10.6 and 14.3 ppm respectively (tables 6-11 and 6-14). These results suggest that there were either instrumental or digestion problems for Ni by this technique.

Several of the other reference materials showed single exceedances for one or two elements on the precision charts. For example, in the standard DGPM, Ce showed an exceed-ance of 82 percent RSD, and a low percent recovery of 70 percent and Zn had a value of 55 percent RSD. Calcium had a slightly elevated RSD in SAR–M of 22 percent, and the RSD for Sb in PB–SMM was 56 percent. Because these exceedances are limited to one reference material, they do not indicate systematic biases or imply quality issues with the analytical technique.

The data accuracy quality control charts for ICPAES–MS55 (figs. 6-7, 6-13, 6-19, 6-25, and 6-31) show very good results. Other than Ni, most values fall within the 85–115 percent recovery control limits. The exceptions were Ti and Y above 115 percent in SAR–L (fig. 6-7); Eu, Ni, and Y above 115 percent and Ho and W below 85 percent in SAR–M (fig. 6-13); Ca and Cd below 85 percent in DGPM (fig. 6-19); and Hf and Zr above 115 percent in GSP–QC (fig. 6-25). System-atic biases were not noted (except for Ni).

Various Single-Element Methods

As part of a current USGS analytical chemistry contract with SGS Minerals, several of the single-element methods are evaluated based on a 20 percent RSD rather than the more conservative 15 percent RSD used for the multielement meth-ods. This difference is shown on the appropriate data preci-sion quality control charts in Appendix 6 (figs. 6-3, 6-8, 6-14, 6-20, 6-26, and 6-32). Most of the quality control statistics (tables 6-3, 6-6, 6-9, 6-12, 6-15, and 6-18) for these elements and methods were at or below 20 percent RSD. The only element or compound other than Au that exceeded the control limit in analytical duplicates is percent CO2 (fig. 6-3) at 25 percent RSD, and in Pebble project SRM PB–SMM (fig. 6-32) at 28 percent RSD.

The data accuracy quality control charts for single-element methods (figs. 6-9, 6-15, 6-21, 6-27, and 6-33) show good results. Percent CO2 exceeds the 115 percent recovery control limit in SAR–M (fig. 6-15), percent organic C exceeds the 115 percent limit in SAR–L (fig. 6-9) and SAR–M (fig. 6-15), and percent total C exceeds the 115 percent limit in SAR–M (fig. 6-15), DGPM (fig. 6-21), and GSP–QC (fig. 6-27).

Activation Laboratories, Ltd., High-Resolution ICP–MS Analysis of Waters

Pond, seep, drill hole and stream water samples were submitted to Activation Labs for analysis by their High-Resolution ICP–MS method. Three quality control samples of standard reference material NIST–1643e were inserted by Activation Labs into the batch. Sixteen additional quality control samples were submitted by the USGS: eight samples of the USGS standard reference material T–159, and eight samples of the USGS standard reference material T–177.


Appendix 7 contains three tables of summary statistics for quality control samples analyzed by the Activation Labs High-Resolution ICP–MS method: SRM NIST–1643e (table 7-1), USGS SRM T–159 (table 7-2), and USGS SRM T–177 (table 7-3). These results are also represented in six quality control charts: precision (percent RSD) of laboratory SRM NIST–1643e (fig. 7-1), accuracy (percent recovery) of labora-tory SRM NIST–1643e (fig. 7-2), precision of USGS SRM T–159 (fig 7-3), accuracy of USGS SRM T–159 (fig. 7-4), precision of USGS SRM T–177 (fig 7-5), and accuracy of USGS SRM T–177 (fig. 7-6).

The analytical table (table 7-1) and graphs of laboratory SRM NIST–1643e show well-constrained results. The graph of analytical precision of SRM NIST–1643e (fig. 7-1) shows that Cd, Cs, Ga, Hf, and W (whose means are more than five times their reporting limits) are above 15 percent RSD. All other ele-ments are below 15 percent, with most of these below 5 percent. The graph of accuracy of SRM NIST–1643e (fig. 7-2) shows all elements with a target value to be very close to 100 percent recovery, and none exceeds the 85–115 percent control limits.

The analytical table (table 7-2) and graphs of USGS SRM T–159 show considerably greater variation, but for different elements than SRM NIST–1643e. The graph of analytical precision of USGS SRM T–159 (fig. 7-3) shows values above 15 percent RSD for Ce, Eu, Gd, Ge, Hf, La, Li, Lu, Mg, Na, Nb, Pr, Tb, Th, Y, and Zr. Of these, Eu and Hf have the high-est values near 60 percent, and the other values range between 20 and 50 percent. The graph of percent recovery for USGS SRM T–159 (fig. 7-4) shows element recovery exceeding the 85–115 percent control limits for As, Be, Cd, Na, and Zn, with As at over 140 percent. Most elements within the 85–115 percent control limits have a slight upward bias between about 100 percent and 115 percent recovery.

The analytical table (table 7-3) and graphs of USGS SRM T–177 show similar results to those of USGS SRM T–159. The graph of analytical precision for USGS SRM T–177 (fig. 7-5) shows values above 15 percent RSD for As, Ce, Eu, Fe, Ga, Gd, Ge, Hf, La, Li, Nb, Pd, Tb, Th, Ti, and Zr. Of these, Th and W greatly exceed the control limit near 90 percent, while the other excessive values range between 15 and 50 per-cent. All other elements are at or below the 15 percent limit, with most below 10 percent. The graph of accuracy for USGS SRM T–177 (fig. 7-6) shows a similar pattern to that for USGS SRM T–159. Element recovery exceeding the 85–115 percent control limits are evident for As, Be, Cd, Fe, Li, and Zn.

Many of the published recommended values were obtained with instrumentation whose detection limits were 10 or more times higher than the new High-Resolution ICP–MS affords. Therefore, those target values may have been determined near instrumental reporting limits, and subject to high uncertainty. Calculation of percent recovery statistics using these low-preci-sion target values and the current analyses may result in spuri-ous high recovery numbers. The low reporting limits obtainable by High-Resolution ICP–MS may necessitate the development of new SRMs, or the re-certification of existing ones.

USGS Laboratories Analysis of Waters

U.S. Geological Survey laboratories performed miscel-laneous tests on water samples, including ferrous/ferric iron (Fe+2/Fe+3) by ferrozine spectrophotometry, dissolved organic carbon by combustion-infrared analysis, and anions and alka-linity by ion chromatography and titration, respectively.

Appendix 8 contains three tables of summary statistics for quality control samples: analytical duplicates of ferrozine aque-ous ferrous and total iron analysis and dissolved organic carbon (DOC) (table 8-1), analytical duplicates of aqueous anions and alkalinity (table 8-2), and quality statistics for USGS standard reference material M–158 (table 8-3). These results are also represented in four quality control charts: precision (percent RSD) of duplicate pairs of ferrozine iron analysis and DOC (fig. 8-1), precision of duplicate pairs of anions and alkalinity analyses (fig. 8-2), precision of USGS standard reference mate-rial M–158 (fig. 8-3), and accuracy (percent recovery) of USGS standard reference material M–158 (fig. 8-4).

Total/Ferrous Iron in Water by Ferrozine AnalysisFour analytical duplicate pairs were chosen from the

water samples for quality control analysis. Total iron analy-ses, whereby all iron in a sample is converted to ferrous iron by hydroxylamine hydrochloride reagent, returned a low RSD of 5.4 percent (table 8-1). Duplicate pairs analyzed for total/ferrous iron (table 8-1) show a percent RSD of 17 percent for ferrous iron. Since the ferric iron concentration is determined by subtraction of the ferrous concentration from the total iron analysis, high contributions to the variations can occur when near the respective reporting limits. Therefore the reported percent RSD of 31 for ferric iron is misleading.

Dissolved Organic Carbon in Water by Combustion-Infrared Analysis

The same four analytical duplicate pairs chosen for iron analysis were also used for analysis of dissolved organic carbon. The data accuracy graph for duplicate pairs (fig. 8-1) shows good results; the value is 6.8 percent RSD.

Anions by Ion Chromatography and Alkalinity by Titration in Water Samples

Nine analytical duplicate pairs were chosen from the water samples for quality control analysis. The precision graph of duplicate pairs analyzed for anions and alkalinity (fig. 8-2) show good results for anions with a mean above 5 times the reporting limit; Cl– is 9.2 percent RSD, SO4

–2 is about 2 percent RSD, and alkalinity is 1.6 percent RSD. The anions F– and NO3

– were both below 5 times the reporting limit. The precision graph for USGS SRM M–158 (fig. 8-3) shows very good results; the only anion that exceeds the 15 percent con-trol limit is F– at 17 percent. Nitrate is at 12 percent and others are near one percent. The accuracy (percent recovery) graph for USGS SRM M–158 (fig. 8-4) shows excellent results; no value exceeds the 85–115 percent control limits.


Summary and Conclusion of the Quality Control Evaluation for the Various Geochemical Data Sets

Quality control evaluations tend to focus on those ele-ments or methods that have problems. This evaluation is no exception. However, it is important to note that this evaluation revealed no precision or accuracy problems for the majority of analytical data from the various laboratories and analytical methods. Therefore, most of these data should be useful for evaluating real variation between sample sites and for assess-ing geochemical signatures of concealed mineralization in the Pebble project area. As is always the case, some care should be taken when interpreting geochemical data based on ele-ments that are frequently reported at concentrations near their lower reporting limits.

Based upon this evaluation of quality control data, the following cautions are given for use in interpreting the analyti-cal data for soils in the Pebble project area. These recommen-dations may not be valid for other data sets, media, or project areas.

• Analytical results that may be used with caution:

• Elements by any method where most of the analyti-cal values are less than five times the corresponding lower reporting limit

• Ti in Ionic Leach

• Sn in ICPAES–MS42 (due to low recoveries from digestion)

• Be in ICPAES–MS42

• Analytical results that should probably not be used:

• Semiquantitative mercury analyses by the Enzyme Leach method are not recommended for use in inter-preting the Pebble project soil results.

• Semiquantitative mercury analyses by the TerraSol leach method are not recommended for use in inter-preting the Pebble project soil results.

• Nickel by ICPAES-MS55

References Cited

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Chao, T.T., 1984, Use of partial dissolution techniques in geo-chemical explortaion: Journal of Geochemical Exploration, v. 20, p. 101–135.

Dux, J.P., 1986, Handbook of quality assurance for the Ana-lytical Chemistry Laboratory: New York, Van Nostrand Reinhold Company Inc., 123 p.

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Kelley, K.D., Eppinger, R.G., Smith, S.M., and Fey, D.L., 2009, Porphyry copper indicator minerals (PCIMs) in gla-cial till samples from the giant Pebble porphyry Cu-Au-Mo deposit: Exploration significance: Proceedings of the 24th International Geochemistry Symposium, Fredericton, New Brunswick, Canada, June 1-4, 2009, p. 361–364..

Lang, J., Payne, J., Rebagliati, M., Roberts, K., Oliver, J., and McLaughlin, J., 2007, The super-giant Pebble copper-gold-molybdenum porphyry deposit, southwest Alaska, in Ores and orogenesis—Circum-Pacific tectonics, geologic evolu-tion, and ore deposits; a symposium honoring the career of William R. Dickinson, Tucson, Ariz., 24 September 2007, Program with abstracts: Tucson, Ariz., Arizona Geological Society, p. 120–121.

Minsley, B., Eppinger, R.G., and Brown, P.J., 2008, Linking self-potential and geochemical signatures over a large por-phyry mineral deposit in Alaska, EOS: Trans. AGU, 89(53), Fall Meeting Abstract #GP43B–0820.

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Pebble Limited Partnership, 2009a, http://www.pebblepartner-ship.com, accessed August 3, 2009.

Pebble Limited Partnership, 2009b, http://www.pebblepartner-ship.com/pages/project-information/CurrentResourceEsti-mates.html, accessed August 3, 2009.

SGS, 2008, Geochem analysis: SGS Mineral Services, 31 p. http://www.sgs.com/min_2008_geochem_analysis_guide.pdf, accessed August 3, 2009.

Skyline Assayers and Laboratories, 2009, 2009 schedule of services and fees: Skyline Assayers and Laboratories, Tuc-son, Ariz., 12 p., http://www.skylinelab.com/docs/Skyline_Labs-2009_Schedule_of_Services_and_Fees-20090220-EN-WEB.pdf, accessed August 3, 2009.

Shimadzu Corporation, 1997, Model TOC 5000A instrument manual: Shimadzu Corporation, Kyoto, Japan, 155 p.

Theodorakos, P.M., 2002, Determination of total alkalinity using a preset endpoint (pH 4.5) autotitration system, in Taggart, J.E., ed., Analytical methods for chemical analysis of geologic and other materials: U.S. Geological Survey Open-File Report 02-223, chapter E, 3 p., available online at http://pubs.er.usgs.gov/usgspubs/ofr/ofr02223.

Theodorakos, P.M., d’Angelo, W.M., and Ficklin, W.H., 2002, Fluoride, chloride, nitrate, and sulfate in aqueous solu-tion utilizing AutoSupression chemically suppressed ion chromatography, in Taggart, J.E., ed., Analytical methods for chemical analysis of geologic and other materials: U.S. Geological Survey Open-File Report 02-223, chapter V, 7 p., available online at http://pubs.er.usgs.gov/usgspubs/ofr/ofr02223.

To, T.B., Nordstrom, D.K., Cunningham, K.M., Ball, J.W., and McCleskey, R.B., 1999, New method for the direct deter-mination of dissolved Fe (III) concentration in acid mine waters: Environmental Science and Technology, v.33, p. 807–813.

U.S. Forest Service, 2007, Bailey’s ecoregions and subre-gions of the United States, Puerto Rico, and the U.S. Virgin Islands: National Atlas of the United States, Reston, Va., http://nationalatlas.gov/mld/ecoregp.html, accessed August 3, 2009.

http://www.pebblepartnership.com

http://www.pebblepartnership.com/pages/project-information/CurrentResourceEstimates.html

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http://nationalatlas.gov/mld/ecoregp.html


Appendix 1: Analytical Methods and Reporting Limits

These are abbreviations commonly found in the appendix tables and figures: %, percent; %RSD, percent relative standard deviation; %Recovery, percent recovery; µg/L, micrograms per liter; mg/L, milligrams per liter; n, number of samples; na, not analyzed; NA, not applicable; ppb, parts per billion; ppm, parts per million; RL, reporting limit.

Table 1-1. Water analytical methods and reporting limits.

Activation Laboratories Activation Laboratories

HR ICP–MS HR ICP–MS

ElementReporting

limitUnits Element

Reporting limit

Units

Ag 0.002 μg/L Mn 0.1 μg/L

As 0.04 μg/L Mo 0.004 μg/L

Au 0.007 μg/L Na 20 μg/L

B 2.0 μg/L Nb 0.000 μg/L

Ba 0.004 μg/L Nd 0.000 μg/L

Be 0.001 μg/L Ni 0.05 μg/L

Bi 0.000 μg/L Pb 0.003 μg/L

Ca 0.005 μg/L Pr 0.000 μg/L

Cd 0.000 μg/L Rb 0.04 μg/L

Ce 0.002 μg/L Re 0.000 μg/L

Co 0.001 μg/L Sb 0.001 μg/L

Cr 0.006 μg/L Sc 0.01 μg/L

Cs 0.001 μg/L Se 3.0 μg/L

Cu 0.01 μg/L Sm 0.000 μg/L

Dy 0.000 μg/L Sn 0.006 μg/L

Er 0.000 μg/L Sr 0.01 μg/L

Eu 0.000 μg/L Ta 0.001 μg/L

Fe 0.1 μg/L Tb 0.000 μg/L

Ga 0.001 μg/L Te 0.001 μg/L

Gd 0.000 μg/L Th 0.000 μg/L

Ge 0.001 μg/L Ti 0.01 μg/L

Hf 0.000 μg/L Tl 0.000 μg/L

Hg 0.04 μg/L Tm 0.000 μg/L

Ho 0.000 μg/L U 0.000 μg/L

In 0.000 μg/L V 0.000 μg/L

K 1.0 μg/L W 0.001 μg/L

La 0.002 μg/L Y 0.000 μg/L

Li 0.03 μg/L Yb 0.000 μg/L

Lu 0.000 μg/L Zn 0.4 μg/L

Mg 0.2 μg/L Zr 0.001 μg/L

Appendix 1: Analytical Methods and Reporting Limits 21

Table 1-2. U.S. Geological Survey reporting limits for anions, alkalinity, dissolved organic carbon, and ferrous iron.

USGS Laboratories

Reporting

Analyte Limit Units

Cl– <0.08 mg/LFl– <0.08 mg/L

NO3– <0.08 mg/L

SO4-2 <0.08 mg/L

Alkalinity 3 mg/LDOC 0.1 mg/L

Ferrous iron 5 µg/L

Table 1-3a. Soil analytical methods and reporting limits.—Continued

Skyline Labs Skyline Labs

Enzyme Leach Terrsol Leach

ElementReporting

limitUnits Element

Reporting limit

Units

Ag 0.1 ppb Ag 20 ppb

Al 0.5 ppm Al 500 ppb

As 0.1 ppb As 5 ppb

Au 0.005 ppb Au 0.1 ppb

B na na B na na

Ba 0.5 ppb Ba 10 ppb

Be 0.1 ppb Be 0.5 ppb

Bi 0.5 ppb Bi 0.5 ppb

Br 1 ppb Br na na

Ca 0.5 ppm Ca 0.5 ppm

Cd 0.1 ppb Cd 0.5 ppb

Ce 0.01 ppb Ce 0.5 ppb

Cl 1,000 ppb Cl 20,000 ppb

Co 0.2 ppb Co 0.5 ppb

Cr 3 ppb Cr 40 ppb

Cs 0.01 ppb Cs 0.1 ppb

Cu 1 ppb Cu 5 ppb

Dy 0.01 ppb Dy 0.1 ppb

Er 0.01 ppb Er 0.06 ppb

Eu 0.01 ppb Eu 0.05 ppb

Fe 1 ppm Fe 1 ppm





ElementReporting

limitUnits Element

Reporting limit

Units

Ge 0.05 ppb Ge 0.1 ppb

Hf 0.01 ppb Hf 0.1 ppb

Hg 0.1 ppb Hg 0.1 ppb

Ho 0.01 ppb Ho 0.02 ppb

I 0.5 ppb I na na

In 0.01 ppb In 0.2 ppb

K 5 ppm K 5 ppm

La 0.01 ppb La 1 ppb

Li 0.5 ppb Li 0.5 ppb

Lu 0.01 ppb Lu 0.2 ppb

Mg 2 ppm Mg 2 ppm

Mn 0.4 ppb Mn 5 ppb

Mo 0.1 ppb Mo 1 ppb

Na 5 ppm Na 5 ppm

Nb 0.1 ppb Nb 0.4 ppb

Nd 0.01 ppb Nd 0.2 ppb

Ni 1 ppb Ni 10 ppb

Os 0.5 ppb Os 0.1 ppb

P na na P na na

Pb 0.1 ppb Pb 5 ppb

Pd 0.5 ppb Pd 1 ppb

Pr 0.01 ppb Pr 0.2 ppb

Pt 0.5 ppb Pt 1 ppb

Rb 0.1 ppb Rb 0.5 ppb

Re 0.005 ppb Re 0.05 ppb

Rh na na Rh 5 ppb

Ru 0.5 ppb Ru 0.2 ppb

S 10 ppm S 10 ppm

Sb 0.01 ppb Sb 1 ppb

Sc 10 ppb Sc 50 ppb

Se 1 ppb Se 20 ppb

Sm 0.01 ppb Sm 0.1 ppb

Sn 0.2 ppb Sn 10 ppb

Sr 0.1 ppb Sr 1 ppb





ElementReporting

limitUnits Element

Reporting limit

Units

Te 0.5 ppb Te 10 ppb

Th 0.01 ppb Th 0.05 ppb

Ti 10 ppb Ti 20 ppb

Tl 0.005 ppb Tl 0.5 ppb

Tm 0.01 ppb Tm 0.05 ppb

U 0.01 ppb U 0.05 ppb

V 0.1 ppb V 5 ppb

W 0.1 ppb W 10 ppb

Y 0.05 ppb Y 0.2 ppb

Yb 0.01 ppb Yb 0.1 ppb

Zn 5 ppb Zn 20 ppb

Zr 0.1 ppb Zr 0.4 ppb

Table 1-3b. Soil analytical methods and reporting limits.—Continued

ALS Chemex ALS Chemex

cold hydroxylamine Ionic leach

Element Reporting limit Units Element Reporting

limit Units

Ag 0.002 ppm Ag 0.1 ppb

Al 1.0 ppm Al na na

As 0.1 ppm As 1 ppb

Au 0.05 ppm Au 0.02 ppb

B 2 ppm B na na

Ba 0.05 ppm Ba 10 ppb

Be 0.05 ppm Be 0.2 ppb

Bi 0.005 ppm Bi 3 ppb

Br 2.0 ppm Br 2 ppb

Ca 10 ppm Ca 0.2 ppm

Cd 0.01 ppm Cd 1.0 ppb

Ce 0.005 ppm Ce 0.1 ppb

Cl na na Cl na na

Co 0.05 ppm Co 0.3 ppb

Cr 0.05 ppm Cr 1.0 ppb

Cs 0.005 ppm Cs 0.1 ppb






limit Units

Er 0.005 ppm Er 0.1 ppb

Eu 0.005 ppm Eu 0.1 ppb

Fe 5.0 ppm Fe 0.1 ppm

Ga 0.05 ppm Ga 0.5 ppb

Gd 0.005 ppm Gd 0.1 ppb

Ge 0.1 ppm Ge 0.2 ppb

Hf 0.01 ppm Hf 10 ppb

Hg 0.1 ppm Hg 0.1 ppb

Ho 0.005 ppm Ho 0.1 ppb

I 0.1 ppm I 0.01 ppb

In 0.005 ppm In 0.5 ppb

K 5.0 ppm K na na

La 0.005 ppm La 0.1 ppb

Li 0.05 ppm Li 0.2 ppb

Lu 0.005 ppm Lu 0.1 ppb

Mg 1.0 ppm Mg 0.01 ppm

Mn 0.1 ppm Mn 0.01 ppm

Mo 0.01 ppm Mo 5.0 ppb

Na 10 ppm Na na na

Nb 0.01 ppm Nb 0.1 ppb

Nd 0.005 ppm Nd 0.1 ppb

Ni 0.05 ppm Ni 3.0 ppb

Os na na Os na na

P 5.0 ppm P na na

Pb 0.1 ppm Pb 10 ppb

Pd na na Pd na na

Pr 0.005 ppm Pr 0.1 ppb

Pt na na Pt na na

Rb 0.01 ppm Rb 5.0 ppb

Re 0.001 ppm Re 0.1 ppb

Rh na na Rh na na

Ru na na Ru na na

S na na S na na






limit Units

Sr 0.05 ppm Sr 10 ppb

Ta 0.01 ppm Ta 10 ppb

Tb 0.005 ppm Tb 0.1 ppb

Te 0.05 ppm Te 1.0 ppb

Th 0.01 ppm Th 1.0 ppb

Ti 1.0 ppm Ti 10 ppb

Tl 0.005 ppm Tl 10 ppb

Tm 0.005 ppm Tm 0.1 ppb

U 0.005 ppm U 1.0 ppb

xV 0.05 ppm V na na

W 0.01 ppm W 0.2 ppb

Y 0.005 ppm Y 0.1 ppb

Yb 0.005 ppm Yb 0.1 ppb

Zn 0.2 ppm Zn 20 ppb

Table 1-3c. Soil analytical methods and reporting limits.—Continued

SGS Minerals SGS Minerals

ICPAES-MS42 acid ICPAES-MS55 sinter


limit Units

Ag 1.0 ppm Ag 1.0 ppm

Al 0.01 % Al 0.01 %

As 1.0 ppm As 30 ppm

Au na na Au na na

B na na B na na

Ba 5.0 ppm Ba 0.5 ppm

Be 0.1 ppm Be 5.0 ppm

Bi 0.04 ppm Bi 0.1 ppm

Br na na Br na na

Ca 0.01 % Ca 0.01 %

Cd 0.1 ppm Cd 0.2 ppm

Ce 0.05 ppm Ce 0.1 ppm

Cl na na Cl na na

Co 0.1 ppm Co 0.5 ppm






limit Units

Cu 0.5 ppm Cu 5.0 ppm

Dy na na Dy 0.05 ppm

Er na na Er 0.05 ppm

Eu na na Eu 0.05 ppm

Fe 0.01 % Fe 0.01 %

Ga 0.05 ppm Ga 1.0 ppm

Gd na na Gd 0.05 ppm

Ge na na Ge 1.0 ppm

Hf na na Hf 1.0 ppm

Hg na na Hg na na

Ho na na Ho 0.05 ppm

I na na I na na

In 0.02 ppm In 0.2 ppm

K 0.01 % K 0.01 %

La 0.5 ppm La 0.1 ppm

Li 1.0 ppm Li 10 ppm

Lu na na Lu 0.05 ppm

Mg 0.01 % Mg 0.01 %

Mn 5.0 ppm Mn 10 ppm

Mo 0.05 ppm Mo 2.0 ppm

Na 0.01 % Na na na

Nb 0.1 ppm Nb 1.0 ppm

Nd na na Nd 0.1 ppm

Ni 0.5 ppm Ni 5.0 ppm

Os na na Os na na

P 50 ppm P 0.01 %

Pb 0.5 ppm Pb 5.0 ppm

Pd na na Pd na na

Pr na na Pr 0.05 ppm

Pt na na Pt na na

Rb na na Rb 0.2 ppm

Re na na Re na na

Rh na na Rh na na

Ru na na Ru na na

S 0.01 % S na na

Appendix 2: Quality Control Tables and Charts for Skyline Assayers and Laboratories Enzyme Leach Data 27





limit Units

Se na na Se na na

Sm na na Sm 0.1 ppm

Sn 0.1 ppm Sn 1.0 ppm

Sr 0.5 ppm Sr 0.1 ppm

Ta na na Ta 0.5 ppm

Tb na na Tb 0.1 ppm

Te 0.1 ppm Te na na

Th 0.2 ppm Th 0.1 ppm

Ti 0.01 % Ti 0.01 %

Tl 0.1 ppm Tl 0.5 ppm

Tm na na Tm 0.05 ppm

U 0.1 ppm U 0.05 ppm

V 1.0 ppm V 5.0 ppm

W 0.1 ppm W 1.0 ppm

Y 0.1 ppm Y 0.5 ppm

Yb na na Yb 0.1 ppm

Zn 1.0 ppm Zn 5.0 ppm

Zr na na Zr 0.5 ppm

Appendix 2: Quality Control Tables and Charts for Skyline Assayers and Laboratories Enzyme Leach Data

Table 2-1. Summary statistics for assessing analytical variation on duplicate samples; determined by an enzyme leach of soil samples at Skyline Labs.—Continued

Element1 UnitsReporting

Limit Pairs (k) Minimum Maximum Mean

Standard Deviation for Duplicates %RSD

Ag ppb 0.1 14 <0.1 0.941 0.159 0.023 14.5Al ppm 0.5 14 1.37 261 98 8.07 8.24As ppb 0.1 14 <0.1 104 11.8 4.02 34.1Au ppb 0.005 14 <0.005 0.122 0.028 0.005 19.3Ba ppb 0.5 14 398 4,410 1,580 99.7 6.31Be ppb 0.1 14 0.24 7.8 2.93 0.436 14.9Bi ppb 0.5 14 <0.5 <0.5 <0.5 NA NA

Br ppb 1.0 14 17.1 636 103 9.03 8.76Ca ppm 0.5 14 9.77 539 169 13.8 8.14






Cd ppb 0.1 14 <0.1 4.75 1.27 0.205 16.1Ce ppb 0.01 14 0.194 68.6 13.3 2.53 18.9Cl ppb 1,000 14 <1,000 20,300 7,790 2,450 31.4Co ppb 0.2 14 1.71 138 34.4 3.35 9.74Cr ppb 3.0 14 <3 6.32 <3 NA NACs ppb 0.01 14 0.184 1.84 0.543 0.022 4.09Cu ppb 1.0 14 <1 262 47.1 10.8 22.9Dy ppb 0.01 14 0.014 9 1.78 0.248 13.9Er ppb 0.01 14 <0.01 4.94 1.02 0.166 16.2Eu ppb 0.01 14 <0.01 2.85 0.535 0.087 16.2Fe ppm 1.0 14 2.33 150 22.9 6.3 27.5Ga ppb 0.3 14 <0.3 4.98 1.3 0.284 21.9Gd ppb 0.01 14 <0.01 11.6 2.18 0.379 17.3Ge ppb 0.05 14 <0.05 0.995 0.309 0.033 10.6Hf ppb 0.01 14 0.012 1.91 0.427 0.053 12.5Hg ppb 0.1 14 <0.1 0.586 0.239 0.064 26.6Ho ppb 0.01 14 0.019 1.68 0.351 0.057 16.1I ppb 0.5 14 <0.5 167 22 2.95 13.4

In ppb 0.01 14 <0.01 0.051 0.016 0.004 27.9K ppm 5.0 14 <5 50.1 9.51 0.698 7.34La ppb 0.01 14 0.169 28.2 6.27 1.16 18.4Li ppb 0.5 14 1.47 21.3 7.78 0.581 7.47Lu ppb 0.01 14 <0.01 0.55 0.123 0.021 17.3Mg ppm 2.0 14 <2 102 33.1 3.11 9.39Mn ppb 0.4 14 36.4 20,800 3,900 366 9.37Mo ppb 0.1 14 0.398 97.2 13.4 5.67 42.4Na ppm 5.0 14 <5 41.5 15.6 1.05 6.73Nb ppb 0.1 14 0.168 1.94 0.621 0.076 12.2Nd ppb 0.01 14 0.278 44.6 8.66 1.47 17Ni ppb 1.0 14 1.45 83.2 28.1 4.15 14.8Os ppb 0.5 14 <0.5 <0.5 <0.5 NA NAPb ppb 0.1 14 <0.1 4.72 0.762 0.576 75.6Pd ppb 0.5 14 <0.5 0.553 <0.5 NA NAPr ppb 0.01 14 0.034 10 1.99 0.331 16.6Pt ppb 0.5 14 <0.5 <0.5 <0.5 NA NARb ppb 0.1 14 8.35 116 29.1 1.87 6.42Re ppb 0.005 14 <0.005 0.123 0.013 0.003 19Ru ppb 0.5 14 <0.5 <0.5 <0.5 NA NAS ppm 10 14 <10 36.4 18.3 3.17 17.3

Sb ppb 0.01 14 0.086 4.23 1.01 0.152 15.1Sc ppb 10 14 <10 29.4 14 1.82 13






Se ppb 1.0 14 <1 9.03 2.18 0.741 33.9Sm ppb 0.01 14 0.111 10.6 2.06 0.282 13.7Sn ppb 0.2 14 <0.2 0.454 0.206 0.045 21.7Sr ppb 0.1 14 37.7 6170 1820 80.1 4.41Ta ppb 0.02 14 <0.02 1 0.289 0.179 62Tb ppb 0.01 14 0.012 1.68 0.367 0.054 14.6Te ppb 0.5 14 <0.5 <0.5 <0.5 NA NATh ppb 0.01 14 <0.01 1.57 0.401 0.046 11.6Ti ppb 10 14 173 5,950 1,250 288 23Tl ppb 0.005 14 0.103 4.46 1 0.048 4.76

Tm ppb 0.01 14 0.013 0.646 0.138 0.022 15.5U ppb 0.01 14 0.016 2.99 0.434 0.025 5.7V ppb 0.1 14 4.98 1,530 233 50.2 21.5W ppb 0.1 14 <0.1 1.87 0.425 0.19 44.8Y ppb 0.05 14 0.29 45.4 9.89 1.7 17.2

Yb ppb 0.01 14 0.066 3.83 0.841 0.118 14Zn ppb 5.0 14 <5 843 136 32.7 24.1Zr ppb 0.1 14 0.823 56.2 15 1.32 8.8

1Skyline Labs considers enzyme leach analyses of Al, Ca, Cl, Cr, Fe, Ga, Ge, Hg, K, Li, Mg, Na, S, Sc, and Ti to be semi-quantitative.

Analysis of Analytical PrecisionEnzyme Leach of Soils (Skyline Assayers and Laboratories)

based on analytical duplicate pairs

0

10

20

30

40

50

60

70

80

Ag_

ppb

*Al_

ppm

As_

ppb

Au_

ppb

Ba_

ppb

Be_

ppb

Bi_

ppb

Br_

ppb

*Ca_

ppm

Cd_

ppb

Ce_

ppb

*Cl_

ppb

Co_

ppb

*Cr_

ppb

Cs_

ppb

Cu_

ppb

Dy_

ppb

Er_

ppb

Eu_

ppb

*Fe_

ppm

*Ga_

ppb

Gd_

ppb

*Ge_

ppb

Hf_

ppb

*Hg_

ppb

Ho_

ppb

I_pp

bIn

_ppb

*K_p

pmLa

_ppb

*Li_

ppb

Lu_p

pb*M

g_pp

mM

n_pp

bM

o_pp

b*N

a_pp

mN

b_pp

bN

d_pp

bN

i_pp

bO

s_pp

bP

b_pp

bP

d_pp

bP

r_pp

bP

t_pp

bR

b_pp

bR

e_pp

bR

u_pp

b*S

_ppm

Sb_

ppb

*Sc_

ppb

Se_

ppb

Sm

_ppb

Sn_

ppb

Sr_

ppb

Ta_p

pbTb

_ppb

Te_p

pbTh

_ppb

*Ti_

ppb

Tl_p

pbTm

_ppb

U_p

pbV

_ppb

W_p

pbY

_ppb

Yb_

ppb

Zn_p

pbZr

_ppb

Elements

% R

SD

Mean >5 x RLMean <5 x RLBelow RLControl Limit

Figure 2-1. Precision plot for 14 analytical duplicate sample pairs by enzyme leach.1

1Values for elements designated with an asterisk (*) are considered semi-quantitative.


Table 2-2. Summary statistics for assessing analytical variation on the standard reference material QAlqt; determined by an enzyme leach of soil samples at Skyline Labs.—Continued


Limit nTarget Value Mean

Standard Deviation %RSD %Recovery

Ag ppb 0.1 6 3.16 2.81 0.206 7.32 89Al ppm 0.5 6 59.9 73.8 4.32 5.85 123As ppb 0.1 6 420 359 32.2 8.96 85.5Au ppb 0.005 6 0.441 0.354 0.029 8.1 80.4Ba ppb 0.5 6 15,300 16,000 1,060 6.66 104Be ppb 0.1 6 8.77 9.29 0.918 9.88 106Bi ppb 0.5 6 2.53 1.94 0.281 14.5 76.5Br ppb 1.0 6 286 340 8.24 2.43 119Ca ppm 0.5 6 2850 3140 311 9.89 110Cd ppb 0.1 6 18.2 25.6 0.709 2.77 141Ce ppb 0.01 6 156 283 3.66 1.29 181Cl ppb 1,000 6 13,900 18,100 2,410 13.4 130Co ppb 0.2 6 597 681 15.9 2.34 114Cr ppb 3.0 6 667 204 6.26 3.07 30.6Cs ppb 0.01 6 0.371 0.309 0.014 4.51 83.4Cu ppb 1.0 6 65.8 118 2.51 2.12 180Dy ppb 0.01 6 23.9 42.3 1.01 2.39 177Er ppb 0.01 6 13.9 22.6 0.96 4.24 163Eu ppb 0.01 6 5.79 10.6 0.167 1.58 182Fe ppm 1.0 6 288 252 12.8 5.06 87.6Ga ppb 0.3 6 16.1 25.9 0.864 3.34 161Gd ppb 0.01 6 28 51.6 1.39 2.7 184Ge ppb 0.05 6 11.5 16.4 0.348 2.13 142Hf ppb 0.01 6 9.29 13.5 0.456 3.38 145Hg ppb 0.1 6 0.258 1.68 0.394 23.5 649Ho ppb 0.01 6 4.83 8.3 0.244 2.94 172I ppb 0.5 6 265 248 6.43 2.59 93.5

In ppb 0.01 6 0.045 0.046 0.011 23.2 102K ppm 5.0 6 151 187 28.6 15.3 124La ppb 0.01 6 60 98.2 3.45 3.52 164Li ppb 0.5 6 405 543 24.9 4.59 134Lu ppb 0.01 6 1.96 3 0.153 5.09 153Mg ppm 2.0 6 213 344 23.8 6.94 161Mn ppb 0.4 6 112,000 130,000 7,970 6.14 116Mo ppb 0.1 6 158 262 31.6 12 166Na ppm 5.0 6 116 119 6.09 5.11 103Nb ppb 0.1 6 22.4 29.1 0.435 1.49 130Nd ppb 0.01 6 98.3 179 6.38 3.55 183Ni ppb 1.0 6 381 486 12.4 2.56 128Os ppb 0.5 6 0.5 <0.5 NA NA 2.02Pb ppb 0.1 6 107 76.8 8.68 11.3 71.8


Table 2-2. Summary statistics for assessing analytical variation on the standard reference material QAlqt; determined by an enzyme leach of soil samples at Skyline Labs.—Continued




Pd ppb 0.5 6 6.37 8.84 1.31 14.9 139Pr ppb 0.01 6 20.2 36.9 0.8 2.17 183Pt ppb 0.5 6 0.5 <0.5 NA NA 60.8Rb ppb 0.1 6 50.1 67.8 2.2 3.24 135Re ppb 0.005 6 0.207 0.197 0.013 6.57 95.3Ru ppb 0.5 6 0.5 <0.5 NA NA 21.8S ppm 10 6 56.8 71 4.91 6.91 125

Sb ppb 0.01 6 199 249 5.22 2.09 125Sc ppb 10 6 158 248 28.4 11.5 157Se ppb 1.0 6 27.1 28 3.18 11.4 103Sm ppb 0.01 6 25.8 47.7 1.05 2.2 185Sn ppb 0.2 6 4.4 5.66 1.13 20 129Sr ppb 0.1 6 21,100 22,000 1,230 5.58 104Ta ppb 0.02 6 4.78 4.08 0.32 7.85 85.3Tb ppb 0.01 6 4.3 7.7 0.18 2.34 179Te ppb 0.5 6 2.67 4.66 0.84 18 175Th ppb 0.01 6 47.5 57.4 0.782 1.36 121Ti ppb 10 6 4,100 5,960 150 2.52 145Tl ppb 0.005 6 0.514 0.706 0.023 3.31 137

Tm ppb 0.01 6 1.86 2.96 0.067 2.25 159U ppb 0.01 6 6.56 6.92 0.196 2.84 105V ppb 0.1 6 716 798 18.1 2.27 111W ppb 0.1 6 275 563 12.5 2.22 205Y ppb 0.05 6 125 218 5.49 2.52 174

Yb ppb 0.01 6 12.2 19.1 0.705 3.69 157Zn ppb 5.0 6 485 541 13.7 2.54 112Zr ppb 0.1 6 372 600 29.8 4.96 161




based on Standard Reference Material QAlqt

0

5

10

15

20

25

Ag_

ppb

*Al_

ppm

As_

ppb

Au_

ppb

Ba_

ppb

Be_

ppb

Bi_

ppb

Br_

ppb

*Ca_

ppm

Cd_

ppb

Ce_

ppb

*Cl_

ppb

Co_

ppb

*Cr_

ppb

Cs_

ppb

Cu_

ppb

Dy_

ppb

Er_

ppb

Eu_

ppb

*Fe_

ppm

*Ga_

ppb

Gd_

ppb

*Ge_

ppb

Hf_

ppb

*Hg_

ppb

Ho_

ppb

I_pp

bIn

_ppb

*K_p

pmLa

_ppb

*Li_

ppb

Lu_p

pb*M

g_pp

mM

n_pp

bM

o_pp

b*N

a_pp

mN

b_pp

bN

d_pp

bN

i_pp

bO

s_pp

bP

b_pp

bP

d_pp

bP

r_pp

bP

t_pp

bR

b_pp

bR

e_pp

bR

u_pp

b*S

_ppm

Sb_

ppb

*Sc_

ppb

Se_

ppb

Sm

_ppb

Sn_

ppb

Sr_

ppb

Ta_p

pbTb

_ppb

Te_p

pbTh

_ppb

*Ti_

ppb

Tl_p

pbTm

_ppb

U_p

pbV

_ppb

W_p

pbY

_ppb

Yb_

ppb

Zn_p

pbZr

_ppb

Elements

% R

SD


Figure 2-2. Precision plot for six analyses of standard reference material QAlqt by enzyme leach.1 %RSD is percent relative standard deviation; RL is reporting limit.

1Values for elements designated with an asterisk (*) are considered semiquantitative.

Analysis of Analytical AccuracyEnzyme Leach of Soils (Skyline Assayers and Laboratories)


0

50

100

150

200

250

Ag_p

pb*A

l_pp

mAs

_ppb

Au_p

pbBa

_ppb

Be_p

pbBi

_ppb

Br_p

pb*C

a_pp

mC

d_pp

bC

e_pp

b*C

l_pp

bC

o_pp

b*C

r_pp

bC

s_pp

bC

u_pp

bD

y_pp

bEr

_ppb

Eu_p

pb*F

e_pp

m*G

a_pp

bG

d_pp

b*G

e_pp

bH

f_pp

b*H

g_pp

bH

o_pp

bI_

ppb

In_p

pb*K

_ppm

La_p

pb*L

i_pp

bLu

_ppb

*Mg_

ppm

Mn_

ppb

Mo_

ppb

*Na_

ppm

Nb_

ppb

Nd_

ppb

Ni_

ppb

Os_

ppb

Pb_p

pbPd

_ppb

Pr_p

pbPt

_ppb

Rb_

ppb

Re_

ppb

Ru_

ppb

*S_p

pmSb

_ppb

*Sc_

ppb

Se_p

pbSm

_ppb

Sn_p

pbSr

_ppb

Ta_p

pbTb

_ppb

Te_p

pbTh

_ppb

*Ti_

ppb

Tl_p

pbTm

_ppb

U_p

pbV_

ppb

W_p

pbY_

ppb

Yb_p

pbZn

_ppb

Zr_p

pb

Elements

% R

ecov

ery

Mean >5 x RLMean <5 x RL85% Recovery115% Recovery

Figure 2-3. Accuracy plot for six analyses of standard reference material QAlqt by enzyme leach.1 RL is reporting limit.

1The percent Recovery for Hg (not shown above) is 650%. Values for elements designated with an asterisk (*) are considered semiquantitative.


Table 2-3. Summary statistics for assessing analytical variation on the standard reference material QRd; determined by an enzyme leach of soil samples at Skyline Labs.—Continued




Ag ppb 0.1 6 0.991 0.46 0.043 9.33 46.5Al ppm 0.5 6 22.2 19.3 0.695 3.59 87.1As ppb 0.1 6 94.1 93.5 9.27 9.92 99.4Au ppb 0.005 6 5.3 3.37 0.164 4.87 63.6Ba ppb 0.5 6 4,130 3,940 174 4.43 95.3Be ppb 0.1 6 4.42 5.29 0.395 7.46 120Bi ppb 0.5 6 2.2 0.877 0.105 11.9 39.8Br ppb 1.0 6 644 670 17.6 2.63 104Ca ppm 0.5 6 1,160 1,120 107 9.55 96.6Cd ppb 0.1 6 5.59 5.72 0.242 4.24 102Ce ppb 0.01 6 58.2 61.1 1.56 2.55 105Cl ppb 1,000 6 155,000 220,000 4,760 2.17 142Co ppb 0.2 6 142 150 3.17 2.11 106Cr ppb 3.0 6 320 72.4 4.23 5.84 22.6Cs ppb 0.01 6 0.44 0.444 0.018 4.04 101Cu ppb 1.0 6 108 100 3.34 3.33 92.8Dy ppb 0.01 6 8.43 9.1 0.269 2.96 108Er ppb 0.01 6 4.44 4.75 0.127 2.66 107Eu ppb 0.01 6 2.13 2.42 0.101 4.19 114Fe ppm 1.0 6 29.5 30.4 1.14 3.76 103Ga ppb 0.3 6 11.7 12 0.616 5.14 102Gd ppb 0.01 6 10.5 11.6 0.41 3.54 110Ge ppb 0.05 6 5.83 6.06 0.181 2.99 104Hf ppb 0.01 6 2.62 2.66 0.109 4.1 102Hg ppb 0.1 6 0.107 0.44 0.152 34.5 411Ho ppb 0.01 6 1.6 1.73 0.053 3.06 108I ppb 0.5 6 222 274 19 6.95 123

In ppb 0.01 6 0.025 0.028 0.007 25.8 110K ppm 5.0 6 107 87.6 13.1 14.9 81.8La ppb 0.01 6 24.8 26.3 0.778 2.96 106Li ppb 0.5 6 193 202 6.1 3.02 105Lu ppb 0.01 6 0.57 0.59 0.022 3.67 104Mg ppm 2.0 6 88.8 94 3.51 3.74 106Mn ppb 0.4 6 21,200 21,500 729 3.39 101Mo ppb 0.1 6 123 160 14.2 8.91 130Na ppm 5.0 6 351 329 13.1 3.98 93.7Nb ppb 0.1 6 3.31 3.31 0.090 2.71 100Nd ppb 0.01 6 39.6 43 1.04 2.43 109Ni ppb 1.0 6 108 104 3.31 3.2 95.9Os ppb 0.5 6 0.5 <0.5 NA NA 100


Table 2-3. Summary statistics for assessing analytical variation on the standard reference material QRd; determined by an enzyme leach of soil samples at Skyline Labs.—Continued




Pb ppb 0.1 6 38.1 32.4 5.86 18.1 85.2Pd ppb 0.5 6 1.85 1.68 0.253 15.1 90.9Pr ppb 0.01 6 8.42 9.29 0.225 2.43 110Pt ppb 0.5 6 0.5 <0.5 NA NA 100Rb ppb 0.1 6 41.3 43.9 0.957 2.18 106Re ppb 0.005 6 0.56 0.552 0.017 3.03 98.6Ru ppb 0.5 6 0.5 <0.5 NA NA 100S ppm 10 6 113 138 8.87 6.44 122

Sb ppb 0.01 6 19.3 21 0.308 1.47 109Sc ppb 10 6 49.2 56.4 6 10.6 115Se ppb 1.0 6 40.6 48.5 6.46 13.3 119Sm ppb 0.01 6 10.1 10.8 0.268 2.47 107Sn ppb 0.2 6 5.04 5.05 0.736 14.6 100Sr ppb 0.1 6 6,690 6,420 339 5.28 96Ta ppb 0.02 6 0.518 0.466 0.089 19.1 90Tb ppb 0.01 6 1.59 1.75 0.105 6 110Te ppb 0.5 6 1.61 1.4 0.363 25.9 87.2Th ppb 0.01 6 4.77 4.68 0.348 7.42 98.2Ti ppb 10 6 1,110 1,160 35.3 3.04 105Tl ppb 0.005 6 0.45 0.538 0.021 3.9 119

Tm ppb 0.01 6 0.565 0.621 0.016 2.56 110U ppb 0.01 6 53.1 50.4 1.57 3.1 95V ppb 0.1 6 463 473 9.82 2.08 102W ppb 0.1 6 53.8 56.9 1.4 2.46 106Y ppb 0.05 6 41.2 45.8 1.01 2.19 111

Yb ppb 0.01 6 3.63 3.83 0.125 3.26 105Zn ppb 5.0 6 194 217 15.2 7.03 112Zr ppb 0.1 6 91.4 89.8 4.45 4.96 98.3




based on Standard Reference Material QRd

0

5

10

15

20

25

30

35

40

Ag_p

pb*A

l_pp

mAs

_ppb

Au_p

pbBa

_ppb

Be_p

pbBi

_ppb

Br_p

pb*C

a_pp

mC

d_pp

bC

e_pp

b*C

l_pp

bC

o_pp

b*C

r_pp

bC

s_pp

bC

u_pp

bD

y_pp

bEr

_ppb

Eu_p

pb*F

e_pp

m*G

a_pp

bG

d_pp

b*G

e_pp

bH

f_pp

b*H

g_pp

bH

o_pp

bI_

ppb

In_p

pb*K

_ppm

La_p

pb*L

i_pp

bLu

_ppb

*Mg_

ppm

Mn_

ppb

Mo_

ppb

*Na_

ppm

Nb_

ppb

Nd_

ppb

Ni_

ppb

Os_

ppb

Pb_p

pbPd

_ppb

Pr_p

pbPt

_ppb

Rb_

ppb

Re_

ppb

Ru_

ppb

*S_p

pmSb

_ppb

*Sc_

ppb

Se_p

pbSm

_ppb

Sn_p

pbSr

_ppb

Ta_p

pbTb

_ppb

Te_p

pbTh

_ppb

*Ti_

ppb

Tl_p

pbTm

_ppb

U_p

pbV_

ppb

W_p

pbY_

ppb

Yb_p

pbZn

_ppb

Zr_p

pb

Elements

% R

SD


Figure 2-4. Precision plot for six analyses of standard reference material QRd by enzyme leach.1 %RSD is percent relative standard deviation; RL is reporting limit.


Analysis of Analytical AccuracyEnzyme Leach of Soils (Skyline Assayers and Laboratories)


0

20

40

60

80

100

120

140

160

Ag_

ppb

*Al_

ppm

As_

ppb

Au_

ppb

Ba_

ppb

Be_

ppb

Bi_

ppb

Br_

ppb

*Ca_

ppm

Cd_

ppb

Ce_

ppb

*Cl_

ppb

Co_

ppb

*Cr_

ppb

Cs_

ppb

Cu_

ppb

Dy_

ppb

Er_

ppb

Eu_

ppb

*Fe_

ppm

*Ga_

ppb

Gd_

ppb

*Ge_

ppb

Hf_

ppb

*Hg_

ppb

Ho_

ppb

I_pp

bIn

_ppb

*K_p

pmLa

_ppb

*Li_

ppb

Lu_p

pb*M

g_pp

mM

n_pp

bM

o_pp

b*N

a_pp

mN

b_pp

bN

d_pp

bN

i_pp

bO

s_pp

bP

b_pp

bP

d_pp

bP

r_pp

bP

t_pp

bR

b_pp

bR

e_pp

bR

u_pp

b*S

_ppm

Sb_

ppb

*Sc_

ppb

Se_

ppb

Sm

_ppb

Sn_

ppb

Sr_

ppb

Ta_p

pbTb

_ppb

Te_p

pbTh

_ppb

*Ti_

ppb

Tl_p

pbTm

_ppb

U_p

pbV

_ppb

W_p

pbY

_ppb

Yb_

ppb

Zn_p

pbZr

_ppb

Elements

% R

ecov

ery


Figure 2-5. Accuracy plot for six analyses of standard reference material QRd by enzyme leach.1 RL is reporting limit.

1The percent Recovery for Hg (not shown above) is 410%. Values for elements designated with an asterisk (*) are considered semiquantitative.


Appendix 3: Quality Control Tables and Charts for Skyline Assayers and Laboratories TerraSol Leach Data

Table 3-1. Summary statistics for assessing analytical variation on duplicate samples; determined by a TerraSol leach of soil samples at Skyline Labs.—Continued




Ag ppb 20 14 <20 108 24.5 0.911 3.72Al ppm 0.5 14 82.5 2,220 809 63.3 7.82As ppb 5 14 <5 269 55 7.07 12.9Au ppb 0.1 14 <0.1 0.186 0.103 0.010 9.98Ba ppb 10 14 217 24,500 4,940 526 10.7Be ppb 0.5 14 2.76 140 23.5 8.05 34.2Bi ppb 0.5 14 <0.5 5.19 0.933 0.151 16.1Ca ppb 0.5 14 3.29 1260 334 28.2 8.44Cd ppm 0.5 14 <0.5 22.5 8.35 1.05 12.6Ce ppb 0.5 14 117 6670 1140 39.3 3.43Cl ppb 20,000 14 <20,000 25,400 <20,000 NA NACo ppb 0.5 14 3.57 464 97.5 11 11.3Cr ppb 40 14 <40 313 57.2 5.28 9.23Cs ppb 0.1 14 0.661 73.7 27.2 1.14 4.2Cu ppb 5 14 21.6 2,820 650 129 19.9Dy ppb 0.1 14 18.1 868 145 26.2 18.1Er ppb 0.06 14 10.6 478 75.8 13.6 17.9Eu ppb 0.05 14 4.3 281 44 5.67 12.9Fe ppb 1 14 25.8 3,840 740 166 22.4Ga ppm 0.5 14 6.01 106 47.3 3.53 7.46Gd ppb 0.7 14 18.6 1,090 172 22 12.8Ge ppb 1 14 <1 7.91 2.19 0.213 9.72Hf ppb 0.1 14 2.34 41.6 10.5 1.27 12.1Hg ppb 0.1 14 <0.1 12 1.1 0.78 70.7Ho ppb 0.02 14 3.73 169 27.7 4.94 17.8In ppb 0.2 14 <0.2 3.85 1.09 0.217 19.8Ir ppb 10 14 <10 <10 <10 NA NAK ppb 5 14 <5 62.5 18.5 1.38 7.45La ppm 1 14 42.2 4,780 572 35.9 6.28Li ppb 2 14 <2 38.2 7.99 0.924 11.6Lu ppb 0.1 14 0.848 49.2 7.66 1.45 18.9Mg ppb 2 14 <2 166 57.7 4.76 8.24Mn ppm 5 14 84.8 50,800 11,200 3,760 33.5Mo ppb 1 14 1.19 214 31.1 3.29 10.6Na ppb 5 14 5.8 69.1 21 3.64 17.3Nb ppm 0.4 14 1.38 29.2 6.73 0.919 13.7Nd ppb 0.2 14 76.3 4,870 720 72.1 10

Appendix 3: Quality Control Tables and Charts for Skyline Assayers and Laboratories TerraSol Leach Data 37

Table 3-1. Summary statistics for assessing analytical variation on duplicate samples; determined by a TerraSol leach of soil samples at Skyline Labs.—Continued




Ni ppb 10 14 <10 317 102 7.51 7.33Os ppb 0.1 14 <0.1 <0.1 <0.1 NA NAPb ppb 5 14 5.21 124 52.1 5.23 10Pd ppb 1 14 <1 9.6 2.59 0.293 11.3Pr ppb 0.2 14 16.9 1,170 170 16.1 9.45Pt ppb 0.1 14 <0.1 0.427 0.125 0.008 6.21Rb ppb 0.5 14 11.7 836 253 8.16 3.23Re ppb 0.05 14 <0.05 0.131 0.051 0.002 4.84Rh ppb 5 14 <5 <5 <5 NA NARu ppb 0.2 14 <0.2 <0.2 <0.2 NA NAS ppm 10 14 <10 67.7 16.6 4.92 29.7

Sb ppb 1 14 <1 4.72 1.72 0.168 9.75Sc ppb 50 14 <50 678 167 16.2 9.69Se ppb 20 14 <20 70.3 26.1 1.98 7.61Sm ppb 0.1 14 17.8 1050 165 22.8 13.8Sn ppb 10 14 <10 <10 <10 NA NASr ppb 1 14 38.3 10,800 2,480 216 8.71Ta ppb 0.1 14 <0.1 1.54 0.374 0.034 8.99Te ppb 10 14 <10 <10 <10 NA NATh ppb 0.05 14 4.55 102 27.4 4.03 14.7Ti ppb 20 14 430 15,100 3,740 363 9.71Tl ppb 0.5 14 <0.5 13 1.34 0.038 2.82

Tm ppb 0.05 14 1.64 59.4 9.65 1.85 19.2U ppb 0.05 14 3.7 225 37.5 13.3 35.3V ppb 5 14 6.26 12,300 1,230 654 53.2W ppb 10 14 <10 <10 <10 NA NAY ppb 0.2 14 113 6,880 906 169 18.6

Yb ppb 0.1 14 10 350 57.7 10.5 18.2Zn ppb 20 14 <20 2,840 346 147 42.4Zr ppb 0.4 14 97.7 1,280 322 45.8 14.2

1Skyline Labs considers TerraSol leach analyses of Al, Ca, Cl, Cr, Fe, Ga, Ge, Hg, K, Li, Mg, Na, S, Sc, and Ti to be semi-quantitative.


Analysis of Analytical PrecisionTerraSol Leach of Soils (Skyline Assayers and Laboratories)


0

10

20

30

40

50

60

70

80

Ag_

ppb

*Al_

ppm

As_

ppb

Au_

ppb

Ba_

ppb

Be_

ppb

Bi_

ppb

*Ca_

ppm

Cd_

ppb

Ce_

ppb

*Cl_

ppb

Co_

ppb

*Cr_

ppb

Cs_

ppb

Cu_

ppb

Dy_

ppb

Er_

ppb

Eu_

ppb

*Fe_

ppm

*Ga_

ppb

Gd_

ppb

*Ge_

ppb

Hf_

ppb

*Hg_

ppb

Ho_

ppb

In_p

pbIr_

ppb

*K_p

pmLa

_ppb

*Li_

ppb

Lu_p

pb*M

g_pp

mM

n_pp

bM

o_pp

b*N

a_pp

mN

b_pp

bN

d_pp

bN

i_pp

bO

s_pp

bP

b_pp

bP

d_pp

bP

r_pp

bP

t_pp

bR

b_pp

bR

e_pp

bR

h_pp

bR

u_pp

b*S

_ppm

Sb_

ppb

*Sc_

ppb

Se_

ppb

Sm

_ppb

Sn_

ppb

Sr_

ppb

Ta_p

pbTe

_ppb

Th_p

pb*T

i_pp

bTl

_ppb

Tm_p

pbU

_ppb

V_p

pbW

_ppb

Y_p

pbY

b_pp

bZn

_ppb

Zr_p

pb

Elements

% R

SD


Figure 3-1. Precision plot for fourteen analytical duplicate sample pairs by TerraSol leach.1 %RSD is percent relative standard deviation; RL is reporting limit.


Table 3-2. Summary statistics for assessing analytical variation on the standard reference material QAlqt; determined by a TerraSol leach of soil samples at Skyline Labs.—Continued




Ag ppb 20 6 NA 39.8 4.17 10.5 NAAl ppm 0.5 6 NA 1,090 75.7 6.94 NAAs ppb 5 6 NA 336 20.3 6.04 NAAu ppb 0.1 6 NA 3.2 0.137 4.27 NABa ppb 10 6 NA 18,800 1,130 6.04 NABe ppb 0.5 6 NA 172 11.3 6.58 NABi ppb 0.5 6 NA 13.7 0.655 4.79 NACa ppm 0.5 6 NA 2,090 153 7.32 NACd ppb 0.5 6 NA 34.2 1.62 4.74 NACe ppb 0.5 6 NA 4,690 292 6.22 NACl ppb 20,000 6 NA 26,800 10,300 38.5 NACo ppb 0.5 6 NA 1,620 92.9 5.75 NACr ppb 40 6 NA 948 60.8 6.42 NACs ppb 0.1 6 NA 18.2 0.965 5.29 NACu ppb 5 6 NA 1,340 68.6 5.11 NADy ppb 0.1 6 NA 470 20.7 4.39 NAEr ppb 0.06 6 NA 273 12 4.4 NA






Eu ppb 0.05 6 NA 130 6.07 4.67 NAFe ppm 1 6 NA 891 55.8 6.26 NAGa ppb 0.5 6 NA 188 10 5.32 NAGd ppb 0.7 6 NA 544 23 4.23 NAGe ppb 1 6 NA 11.2 0.732 6.54 NAHf ppb 0.1 6 NA 70.6 3.26 4.61 NAHg ppb 0.1 6 NA 5.01 1.02 20.4 NAHo ppb 0.02 6 NA 93.3 3.96 4.24 NAIn ppb 0.2 6 NA 1.81 0.105 5.83 NAIr ppb 10 6 NA <10 NA na NAK ppm 5 6 NA 176 15.7 8.91 NALa ppb 1 6 NA 1,450 66.8 4.62 NALi ppb 2 6 NA 476 37.7 7.91 NALu ppb 0.1 6 NA 34.6 1.37 3.97 NAMg ppm 2 6 NA 165 12 7.26 NAMn ppb 5 6 NA 160,000 9,970 6.25 NAMo ppb 1 6 NA 302 17 5.64 NANa ppm 5 6 NA 27.1 2.2 8.14 NANb ppb 0.4 6 NA 54.6 2.75 5.05 NANd ppb 0.2 6 NA 2,500 117 4.68 NANi ppb 10 6 NA 680 41 6.03 NAOs ppb 0.1 6 NA <0.1 NA NA NAPb ppb 5 6 NA 469 20.8 4.42 NAPd ppb 1 6 NA 23.9 2.62 11 NAPr ppb 0.2 6 NA 581 26.9 4.63 NAPt ppb 0.1 6 NA 1.13 0.119 10.5 NARb ppb 0.5 6 NA 317 17.3 5.46 NARe ppb 0.05 6 NA 0.206 0.020 9.68 NARh ppb 5 6 NA <5 NA NA NARu ppm 0.2 6 NA 0.393 0.105 26.7 NAS ppb 10 6 NA 47.6 13 27.2 NA

Sb ppb 1 6 NA 58.8 2.71 4.61 NASc ppb 50 6 NA 889 68.1 7.67 NASe ppb 20 6 NA 89.1 7.02 7.88 NASm ppb 0.1 6 NA 566 24.5 4.32 NASn ppb 10 6 NA <10 NA NA NASr ppb 1 6 NA 16,700 1,060 6.33 NATa ppb 0.1 6 NA 1.44 0.100 6.97 NATe ppb 10 6 NA <10 NA NA NATh ppb 0.05 6 NA 956 48.1 5.04 NATi ppb 20 6 NA 5,060 332 6.58 NA






Tl ppb 0.5 6 NA <0.5 NA NA NATm ppb 0.05 6 NA 38.2 1.59 4.16 NAU ppb 0.05 6 NA 226 11 4.87 NAV ppb 5 6 NA 1,460 98.9 6.78 NAW ppb 10 6 NA 659 31.2 4.74 NAY ppb 0.2 6 NA 2,700 183 6.81 NA

Yb ppb 0.1 6 NA 253 10.7 4.23 NAZn ppb 20 6 NA 682 43 6.32 NAZr ppb 0.4 6 NA 2,280 113 4.95 NA




0

5

10

15

20

25

30

35

40

45

Ag_

ppb

*Al_

ppm

As_

ppb

Au_

ppb

Ba_

ppb

Be_

ppb

Bi_

ppb

*Ca_

ppm

Cd_

ppb

Ce_

ppb

*Cl_

ppb

Co_

ppb

*Cr_

ppb

Cs_

ppb

Cu_

ppb

Dy_

ppb

Er_

ppb

Eu_

ppb

*Fe_

ppm

*Ga_

ppb

Gd_

ppb

*Ge_

ppb

Hf_

ppb

*Hg_

ppb

Ho_

ppb

In_p

pbIr_

ppb

*K_p

pmLa

_ppb

*Li_

ppb

Lu_p

pb*M

g_pp

Mn_

ppb

Mo_

ppb

*Na_

ppm

Nb_

ppb

Nd_

ppb

Ni_

ppb

Os_

ppb

Pb_

ppb

Pd_

ppb

Pr_

ppb

Pt_

ppb

Rb_

ppb

Re_

ppb

Rh_

ppb

Ru_

ppb

*S_p

pmS

b_pp

b*S

c_pp

bS

e_pp

bS

m_p

pbS

n_pp

bS

r_pp

bTa

_ppb

Te_p

pbTh

_ppb

*Ti_

ppb

Tl_p

pbTm

_ppb

U_p

pbV

_ppb

W_p

pbY

_ppb

Yb_

ppb

Zn_p

pbZr

_ppb

Elements

% R

SD


Figure 3-2. Precision plot for six analyses of standard reference material QAlqt by TerraSol leach.1 %RSD is percent relative standard deviation; RL is reporting limit.



Table 3-3. Summary statistics for assessing analytical variation on the standard reference material QRd; determined by a TerraSol leach of soil samples at Skyline Labs.—Continued




Ag ppb 20 6 NA 20.1 1.63 8.09 NAAl ppm 0.5 6 NA 57.5 3.09 5.38 NAAs ppb 5 6 NA 70.3 2.1 2.99 NAAu ppb 0.1 6 NA 0.283 0.038 13.6 NABa ppb 10 6 NA 7,500 240 3.2 NABe ppb 0.5 6 NA 40.1 1.75 4.36 NABi ppb 0.5 6 NA 2.8 0.057 2.02 NACa ppm 0.5 6 NA 838 61.8 7.37 NACd ppb 0.5 6 NA 15.4 0.471 3.06 NACe ppb 0.5 6 NA 3,310 119 3.6 NACl ppb 20,000 6 NA <20,000 NA NA NACo ppb 0.5 6 NA 671 20 2.97 NACr ppb 40 6 NA 54.8 6.99 12.8 NACs ppb 0.1 6 NA 9.25 0.173 1.87 NACu ppb 5 6 NA 324 6.65 2.05 NADy ppb 0.1 6 NA 361 3.08 0.853 NAEr ppb 0.06 6 NA 199 1.63 0.819 NAEu ppb 0.05 6 NA 102 1.1 1.07 NAFe ppm 1 6 NA 40.5 0.935 2.31 NAGa ppb 0.5 6 NA 30.2 1.49 4.92 NAGd ppb 0.7 6 NA 456 6.88 1.51 NAGe ppb 1 6 NA 7.44 0.339 4.56 NAHf ppb 0.1 6 NA 12.1 0.253 2.09 NAHg ppb 0.1 6 NA 9.22 3.2 34.7 NAHo ppb 0.02 6 NA 70.4 0.817 1.16 NAIn ppb 0.2 6 NA 0.249 0.020 7.91 NAIr ppb 10 6 NA <10 NA NA NAK ppm 5 6 NA 138 11.1 8.05 NALa ppb 1 6 NA 1,440 17.2 1.2 NALi ppb 2 6 NA 87.1 3.8 4.36 NALu ppb 0.1 6 NA 21.9 0.327 1.49 NAMg ppm 2 6 NA 139 5.73 4.12 NAMn ppb 5 6 NA 52,200 1,530 2.93 NAMo ppb 1 6 NA 82 1.64 1.99 NANa ppm 5 6 NA 9.56 0.829 8.67 NANb ppb 0.4 6 NA 2.81 0.098 3.49 NANd ppb 0.2 6 NA 2,150 14.7 0.685 NANi ppb 10 6 NA 329 13.5 4.09 NAOs ppb 0.1 6 NA <0.1 NA NA NAPb ppb 5 6 NA 147 1.05 0.716 NA


Table 3-3. Summary statistics for assessing analytical variation on the standard reference material QRd; determined by a TerraSol leach of soil samples at Skyline Labs.—Continued




Pd ppb 1 6 NA 3.1 0.387 12.5 NAPr ppb 0.2 6 NA 503 6.92 1.37 NAPt ppb 0.1 6 NA <0.1 NA NA NARb ppb 0.5 6 NA 224 4.73 2.11 NARe ppb 0.05 6 NA 0.052 0.009 18.2 NARh ppb 0.2 6 NA <0.2 NA NA NARu ppb 0.2 6 NA 0.256 0.083 32.3 NAS ppm 10 6 NA <10 NA NA NA

Sb ppb 1 6 NA 7.15 0.201 2.81 NASc ppb 50 6 NA 122 4.72 3.86 NASe ppb 20 6 NA 41.3 4.99 12.1 NASm ppb 0.1 6 NA 463 4.9 1.06 NASn ppb 10 6 NA <10 NA NA NASr ppb 1 6 NA 5,720 165 2.89 NATa ppb 0.1 6 NA 0.501 0.030 6.01 NATe ppb 10 6 NA <10 NA NA NATh ppb 0.05 6 NA 187 1.94 1.04 NATi ppb 20 6 NA 555 16.1 2.9 NATl ppb 0.5 6 NA <0.5 NA NA NA

Tm ppb 0.05 6 NA 26.1 0.183 0.703 NAU ppb 0.05 6 NA 70.5 0.842 1.19 NAV ppb 5 6 NA 188 6.84 3.64 NAW ppb 10 6 NA 124 3.72 3 NAY ppb 0.2 6 NA 2,030 132 6.48 NA

Yb ppb 0.1 6 NA 159 1.67 1.05 NAZn ppb 20 6 NA 340 8.61 2.53 NAZr ppb 0.4 6 NA 302 7.06 2.34 NA





0

5

10

15

20

25

30

35

40

Ag_p

pb*A

l_pp

mAs

_ppb

Au_p

pbBa

_ppb

Be_p

pbBi

_ppb

*Ca_

ppC

d_pp

bC

e_pp

b*C

l_pp

bC

o_pp

b*C

r_pp

bC

s_pp

bC

u_pp

bD

y_pp

bEr

_ppb

Eu_p

pb*F

e_pp

m*G

a_pp

bG

d_pp

b*G

e_pp

bH

f_pp

b*H

g_pp

bH

o_pp

bIn

_ppb

Ir_pp

b*K

_ppm

La_p

pb*L

i_pp

bLu

_ppb

*Mg_

ppM

n_pp

bM

o_pp

b*N

a_pp

mN

b_pp

bN

d_pp

bN

i_pp

bO

s_pp

bPb

_ppb

Pd_p

pbPr

_ppb

Pt_p

pbR

b_pp

bR

e_pp

bR

h_pp

bR

u_pp

b*S

_ppm

Sb_p

pb*S

c_pp

bSe

_ppb

Sm_p

pbSn

_ppb

Sr_p

pbTa

_ppb

Te_p

pbTh

_ppb

*Ti_

ppb

Tl_p

pbTm

_ppb

U_p

pbV_

ppb

W_p

pbY_

ppb

Yb_p

pbZn

_ppb

Zr_p

pb

Elements

% R

SD


Figure 3-3. Precision plot for six analyses of standard reference material QRd by TerraSol leach.1 %RSD is percent relative standard deviation; RL is reporting limit.


Table 3-4. Summary statistics for assessing analytical variation on the standard reference material PB–SNP; determined by a TerraSol leach of soil samples at Skyline Labs.—Continued




Ag ppb 20 3 NA <20 NA NA NAAl ppm 0.5 3 NA 1,200 37.9 3.16 NAAs ppb 5 3 NA 46.8 6.06 12.9 NAAu ppb 0.1 3 NA <0.1 NA NA NABa ppb 10 3 NA 2,230 5.77 0.259 NABe ppb 0.5 3 NA 34.4 4.26 12.4 NABi ppb 0.5 3 NA 1.59 0.234 14.7 NACa ppm 0.5 3 NA 165 20.8 12.6 NACd ppb 0.5 3 NA 22.3 0.379 1.7 NACe ppb 0.5 3 NA 960 42.2 4.39 NACl ppb 20,000 3 NA <20,000 NA NA NACo ppb 0.5 3 NA 284 7.57 2.66 NACr ppb 40 3 NA 63.9 9.85 15.4 NACs ppb 0.1 3 NA 32.7 0.404 1.24 NACu ppb 5 3 NA 3,150 802 25.5 NADy ppb 0.1 3 NA 134 6.35 4.75 NAEr ppb 0.06 3 NA 67.1 4.55 6.78 NA






Eu ppb 0.05 3 NA 35.2 0.945 2.68 NAFe ppm 1 3 NA 547 66.1 12.1 NAGa ppm 0.5 3 NA 107 5.51 5.16 NAGd ppb 0.7 3 NA 147 2.31 1.57 NAGe ppb 1 3 NA 1.82 0.064 3.5 NAHf ppb 0.1 3 NA 18.1 1.92 10.6 NAHg ppb 0.1 3 NA 0.189 0.17 89.9 NAHo ppb 0.02 3 NA 25.1 1.68 6.69 NAIn ppb 0.2 3 NA 2.12 0.296 14 NAIr ppb 10 3 NA <10 NA NA NAK ppm 5 3 NA 58 5.64 9.71 NALa ppb 1 3 NA 393 25.9 6.58 NALi ppb 2 3 NA 8.39 0.122 1.46 NALu ppb 0.1 3 NA 6.47 0.467 7.22 NAMg ppm 2 3 NA 52.2 5.03 9.63 NAMn ppb 5 3 NA 13,900 513 3.68 NAMo ppb 1 3 NA 15.3 0.656 4.29 NANa ppm 5 3 NA 24.3 1.1 4.51 NANb ppb 0.4 3 NA 11.8 1.49 12.7 NANd ppb 0.2 3 NA 563 11.7 2.08 NANi ppb 10 3 NA 196 17.6 8.97 NAOs ppb 0.1 3 NA <0.1 NA NA NAPb ppb 5 3 NA 123 2.08 1.69 NAPd ppb 1 3 NA 4.74 0.92 19.4 NAPr ppb 0.2 3 NA 131 1.53 1.17 NAPt ppb 0.1 3 NA 0.174 0.021 12 NARb ppb 0.5 3 NA 346 9.81 2.84 NARe ppb 0.05 3 NA 0.126 0.007 5.73 NARh ppb 5 3 NA <5 NA NA NARu ppb 0.2 3 NA <0.2 NA NA NAS ppm 10 3 NA 27.6 4.89 17.7 NA

Sb ppb 1 3 NA 2.7 0.43 16 NASc ppb 50 3 NA 214 26.5 12.4 NASe ppb 20 3 NA 39.4 9.85 25 NASm ppb 0.1 3 NA 137 0.577 0.422 NASn ppb 10 3 NA <10 NA NA NASr ppb 1 3 NA 1,060 62 5.82 NATa ppb 0.1 3 NA 0.644 0.090 14 NATe ppb 10 3 NA <10 NA NA NATh ppb 0.05 3 NA 62.7 6.61 10.5 NATi ppb 20 3 NA 4,370 484 11.1 NA






Tl ppb 0.5 3 NA <0.5 NA NA NATm ppb 0.05 3 NA 8.49 0.6 7.08 NAU ppb 0.05 3 NA 70.7 6.39 9.04 NAV ppb 5 3 NA 161 15.8 9.85 NAW ppb 10 3 NA <10 NA NA NAY ppb 0.2 3 NA 651 34.6 5.32 NA

Yb ppb 0.1 3 NA 50.5 3.85 7.62 NAZn ppb 20 3 NA 581 71.5 12.3 NAZr ppb 0.4 3 NA 543 58.7 10.8 NA



based on Standard Reference Material PB-SNP

0

10

20

30

40

50

60

70

80

90

100

Ag_

ppb

*Al_

ppm

As_

ppb

Au_

ppb

Ba_

ppb

Be_

ppb

Bi_

ppb

*Ca_

ppm

Cd_

ppb

Ce_

ppb

*Cl_

ppb

Co_

ppb

*Cr_

ppb

Cs_

ppb

Cu_

ppb

Dy_

ppb

Er_

ppb

Eu_

ppb

*Fe_

ppm

*Ga_

ppb

Gd_

ppb

*Ge_

ppb

Hf_

ppb

*Hg_

ppb

Ho_

ppb

In_p

pbIr_

ppb

*K_p

pmLa

_ppb

*Li_

ppb

Lu_p

pb*M

g_pp

mM

n_pp

bM

o_pp

b*N

a_pp

mN

b_pp

bN

d_pp

bN

i_pp

bO

s_pp

bP

b_pp

bP

d_pp

bP

r_pp

bP

t_pp

bR

b_pp

bR

e_pp

bR

h_pp

bR

u_pp

b*S

_ppm

Sb_

ppb

*Sc_

ppb

Se_

ppb

Sm

_ppb

Sn_

ppb

Sr_

ppb

Ta_p

pbTe

_ppb

Th_p

pb*T

i_pp

bTl

_ppb

Tm_p

pbU

_ppb

V_p

pbW

_ppb

Y_p

pbY

b_pp

bZn

_ppb

Zr_p

pb

Elements

% R

SD


Figure 3-4. Precision plot for three analyses of standard reference material PB–SNP by TerraSol leach.1 %RSD is percent relative standard deviation; RL is reporting limit.



Appendix 4: Quality Control Tables and Charts for ALS Chemex Cold Hydroxylamine Hydrochloride Leach Data

Table 4-1. Summary statistics for assessing analytical variation on duplicate samples; determined by a cold hydroxylamine hydrochloride leach of soil samples at ALS Chemex.—Continued

Element UnitsReporting



Ag ppm 0.002 5 <0.002 0.037 0.013 0.001 5.6Al ppm 1 5 376 4,670 2,050 245 11.9As ppm 0.1 5 <0.1 0.2 0.107 0.032 29.8Au ppm 0.05 5 <0.05 <0.05 <0.05 NA NAB ppm 2 5 <2 <2 <2 NA NABa ppm 0.05 5 11.2 111 59.6 12.3 20.6Be ppm 0.05 5 <0.05 0.2 0.118 0.020 17.3Bi ppm 0.005 5 <0.005 <0.005 <0.005 NA NABr ppm 2 5 <2 5 2.64 0.322 12.2Ca ppm 10 5 10 12,000 4,220 1,640 38.9Cd ppm 0.01 5 0.01 0.09 0.03 0.009 29.8Ce ppm 0.005 5 0.199 6.76 2.66 0.088 3.28Co ppm 0.05 5 <0.05 0.88 0.358 0.122 34.2Cr ppm 0.05 5 0.05 0.35 0.184 0.016 8.76Cs ppm 0.005 5 <0.005 0.082 0.04 0.002 4.68Cu ppm 0.05 5 <0.05 1.08 0.626 0.025 3.99Dy ppm 0.005 5 0.02 0.983 0.311 0.017 5.43Er ppm 0.005 5 0.012 0.495 0.158 0.004 2.45Eu ppm 0.005 5 0.008 0.272 0.092 0.003 3.51Fe ppm 5 5 216 818 436 111 25.4Ga ppm 0.05 5 0.05 0.24 0.142 0.008 5.45Gd ppm 0.005 5 0.02 1.165 0.368 0.008 2.08Ge ppm 0.1 5 <0.1 <0.1 <0.1 NA NAHf ppm 0.01 5 <0.01 0.05 0.020 0.004 22.8Hg ppm 0.1 5 <0.1 <0.1 <0.1 NA NAHo ppm 0.005 5 <0.005 0.181 0.058 0.002 4.31I ppm 0.1 5 <0.1 4.5 1.25 0.055 4.39

In ppm 0.005 5 <0.005 0.006 <0.005 NA NAK ppm 5 5 8 40 25.6 7.03 27.5La ppm 0.005 5 0.121 4.06 1.52 0.048 3.14Li ppm 0.05 5 <0.05 0.11 0.055 0.013 23Lu ppm 0.005 5 <0.005 0.053 0.018 0.000 1.81Mg ppm 1 5 16 880 287 119 41.5Mn ppm 0.1 5 2.5 53.4 25.1 7.36 29.3Mo ppm 0.01 5 <0.01 0.02 0.011 0.003 30.2Na ppm 10 5 10 40 24 10 41.7Nb ppm 0.01 5 <0.01 0.04 0.017 0.003 19.1

Appendix 4: Quality Control Tables and Charts for ALS Chemex Cold Hydroxylamine Hydrochloride Leach Data 47

Table 4-1. Summary statistics for assessing analytical variation on duplicate samples; determined by a cold hydroxylamine hydrochloride leach of soil samples at ALS Chemex.—Continued




Nd ppm 0.005 5 0.071 4.62 1.48 0.027 1.81Ni ppm 0.05 5 0.07 1.45 0.383 0.139 36.3P ppm 5 5 <5 341 83.6 4.84 5.79

Pb ppm 0.1 5 0.1 0.6 0.29 0.055 18.9Pr ppm 0.005 5 0.02 1.09 0.362 0.014 3.82Rb ppm 0.01 5 0.01 0.7 0.343 0.009 2.77Re ppm 0.001 5 <0.001 0.001 <0.001 NA NASb ppm 0.005 5 <0.005 0.007 <0.005 NA NASe ppm 0.5 5 <0.5 <0.5 <0.5 NA NASm ppm 0.005 5 0.011 1.05 0.326 0.006 1.9Sn ppm 0.05 5 <0.05 <0.05 <0.05 NA NASr ppm 0.05 5 0.3 88.8 32.4 16.6 51.2Ta ppm 0.01 5 <0.01 <0.01 <0.01 NA NATb ppm 0.005 5 <0.005 0.178 0.056 0.002 3.46Te ppm 0.05 5 <0.05 <0.05 <0.05 NA NATh ppm 0.01 5 <0.01 0.04 0.020 0 0Ti ppm 1 5 2 20 7.5 1.05 14Tl ppm 0.005 5 <0.005 0.015 0.009 0.001 9.83

Tm ppm 0.005 5 <0.005 0.07 0.023 0.001 4.26U ppm 0.005 5 <0.005 0.068 0.039 0.006 14.7V ppm 0.05 5 0.15 5 1.75 0.593 33.9W ppm 0.01 5 <0.01 0.01 <0.01 NA NAY ppm 0.005 5 0.164 5.66 1.76 0.104 5.89

Yb ppm 0.005 5 0.01 0.357 0.112 0.006 5.68Zn ppm 0.2 5 0.3 1 0.54 0.141 26.2Zr ppm 0.05 5 <0.05 1.46 0.538 0.035 6.5


Analysis of Analytical PrecisionCold Hydroxylamine Hydrochloride Leach of Soils (ALS Chemex)


0

10

20

30

40

50

60

Ag_

ppm

Al_

ppm

As_

ppm

Au_

ppm

B_p

pmB

a_pp

mB

e_pp

mB

i_pp

mB

r_pp

mC

a_pp

mC

d_pp

mC

e_pp

mC

o_pp

mC

r_pp

mC

s_pp

mC

u_pp

mD

y_pp

mE

r_pp

mE

u_pp

mFe

_ppm

Ga_

ppm

Gd_

ppm

Ge_

ppm

Hf_

ppm

Hg_

ppm

Ho_

ppm

I_pp

mIn

_ppm

K_p

pmLa

_ppm

Li_p

pmLu

_ppm

Mg_

ppm

Mn_

ppm

Mo_

ppm

Na_

ppm

Nb_

ppm

Nd_

ppm

Ni_

ppm

P_p

pmP

b_pp

mP

r_pp

mR

b_pp

mR

e_pp

mS

b_pp

mS

e_pp

mS

m_p

pmS

n_pp

mS

r_pp

mTa

_ppm

Tb_p

pmTe

_ppm

Th_p

pmTi

_ppm

Tl_p

pmTm

_ppm

U_p

pmV

_ppm

W_p

pmY

_ppm

Yb_

ppm

Zn_p

pmZr

_ppm

Elements

% R

SD


Figure 4-1. Precision plot for five analytical duplicate sample pairs by cold hydroxylamine leach. %RSD is percent relative standard deviation; RL is reporting limit.

Table 4-2. Summary statistics for assessing analytical variation on the standard reference material LK4–ALG; determined by a cold hydroxylamine hydrochloride leach of soil samples at ALS Chemex.—Continued




Ag ppm 0.002 2 0.003 0.004 0.002 60.6 117Al ppm 1.0 2 1,740 1,600 28.3 1.77 92As ppm 0.1 2 1.65 1.8 0 0 109Au ppm 0.05 2 0.072 <0.05 NA NA 62.7B ppm 2.0 2 3.9 3 0 0 76.9Ba ppm 0.05 2 11.775 13.3 0.601 4.53 113Be ppm 0.05 2 0.115 0.135 0.007 5.24 117Bi ppm 0.005 2 0.007 <0.005 NA NA 66Br ppm 2.0 2 3.4 2.5 0.707 28.3 73.5Ca ppm 10 2 6,880 7,080 84.9 1.2 103Cd ppm 0.01 2 1.07 1.17 0.014 1.21 109Ce ppm 0.005 2 5.17 5.53 0 0 107Co ppm 0.05 2 2.265 2.38 0.163 6.85 105Cr ppm 0.05 2 0.235 0.31 0.014 4.56 132Cs ppm 0.005 2 0.041 0.05 0.001 2.83 122Cu ppm 0.05 2 1.86 2.06 0.028 1.37 111Dy ppm 0.005 2 0.308 0.347 0.001 0.408 113Er ppm 0.005 2 0.192 0.209 0 0 109






Eu ppm 0.005 2 0.077 0.088 0.001 0.808 114Fe ppm 5.0 2 869 834 75 8.99 96Ga ppm 0.05 2 0.2 0.25 0.014 5.66 125Gd ppm 0.005 2 0.402 0.434 0.004 0.978 108Ge ppm 0.1 2 0.14 <0.1 NA NA 65.1Hf ppm 0.01 2 0.02 0.01 0 0 50Hg ppm 0.1 2 0.14 <0.1 NA NA 65.1Ho ppm 0.005 2 0.065 0.073 0.001 1.94 112I ppm 0.1 2 0.14 0.2 0 0 143

In ppm 0.005 2 0.016 0.023 0.001 3.14 141K ppm 5.0 2 119 132 2.83 2.14 111La ppm 0.005 2 4.075 4.34 0.014 0.326 107Li ppm 0.05 2 0.072 0.085 0.007 8.32 118Lu ppm 0.005 2 0.019 0.026 0.001 2.77 134Mg ppm 1.0 2 429 385 1.41 0.367 89.7Mn ppm 0.1 2 252.5 249 0 0 98.6Mo ppm 0.01 2 0.014 0.01 0 0 71.4Na ppm 10 2 35 30 0 0 85.7Nb ppm 0.01 2 0.014 0.02 0 0 143Nd ppm 0.005 2 2.123 2.26 0 0 106Ni ppm 0.05 2 8.21 8.53 0.346 4.06 104P ppm 5.0 2 142 156 14.1 9.07 110

Pb ppm 0.1 2 20.55 22.2 0.141 0.637 108Pr ppm 0.005 2 0.621 0.661 0.007 1.07 106Rb ppm 0.01 2 0.735 0.785 0.021 2.7 107Re ppm 0.001 2 0.001 0.001 0 0 71.4Sb ppm 0.005 2 0.105 0.118 0.001 0.602 112Se ppm 0.5 2 0.62 <0.5 NA NA 72.8Sm ppm 0.005 2 0.326 0.348 0.006 1.83 107Sn ppm 0.05 2 0.072 <0.05 NA NA 62.7Sr ppm 0.05 2 23.95 25.3 0.283 1.12 106Ta ppm 0.01 2 0.014 <0.01 NA NA 65.1Tb ppm 0.005 2 0.055 0.063 0.002 3.39 114Te ppm 0.05 2 0.072 <0.05 NA NA 62.7Th ppm 0.01 2 0.035 0.035 0.007 20.2 100Ti ppm 1.0 2 2.0 3.0 0 0 150Tl ppm 0.005 2 0.156 0.173 0.004 2.45 111

Tm ppm 0.005 2 0.024 0.030 0.002 7.19 123U ppm 0.005 2 2.38 2.55 0.078 3.06 107V ppm 0.05 2 5 5.14 0.269 5.23 103W ppm 0.01 2 0.014 <0.01 NA NA 65.1






Y ppm 0.005 2 2.885 3.1 0.106 3.43 107Yb ppm 0.005 2 0.149 0.16 0.004 2.65 107Zn ppm 0.2 2 68.45 69.4 3.11 4.48 101Zr ppm 0.05 2 0.102 0.155 0.021 13.7 152


based on Standard Reference Material LK4-ALG

0

10

20

30

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50

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70

Ag_

ppm

Al_

ppm

As_

ppm

Au_

ppm

B_p

pmB

a_pp

mB

e_pp

mB

i_pp

mB

r_pp

mC

a_pp

mC

d_pp

mC

e_pp

mC

o_pp

mC

r_pp

mC

s_pp

mC

u_pp

mD

y_pp

mE

r_pp

mE

u_pp

mFe

_ppm

Ga_

ppm

Gd_

ppm

Ge_

ppm

Hf_

ppm

Hg_

ppm

Ho_

ppm

I_pp

mIn

_ppm

K_p

pmLa

_ppm

Li_p

pmLu

_ppm

Mg_

ppm

Mn_

ppm

Mo_

ppm

Na_

ppm

Nb_

ppm

Nd_

ppm

Ni_

ppm

P_p

pmP

b_pp

mP

r_pp

mR

b_pp

mR

e_pp

mS

b_pp

mS

e_pp

mS

m_p

pmS

n_pp

mS

r_pp

mTa

_ppm

Tb_p

pmTe

_ppm

Th_p

pmTi

_ppm

Tl_p

pmTm

_ppm

U_p

pmV

_ppm

W_p

pmY

_ppm

Yb_

ppm

Zn_p

pmZr

_ppm

Elements

% R

SD


Figure 4-2. Precision plot for two analyses of standard reference material LK4–ALG by cold hydroxylamine leach. %RSD is percent relative standard deviation; RL is reporting limit.


Analysis of Analytical AccuracyCold Hydroxylamine Hydrochloride Leach of Soils (ALS Chemex)

based on Standard Reference Material LK4-ALG

0

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100

120

140

160

Ag_

ppm

Al_

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As_

ppm

Au_

ppm

B_p

pmB

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mB

e_pp

mB

i_pp

mB

r_pp

mC

a_pp

mC

d_pp

mC

e_pp

mC

o_pp

mC

r_pp

mC

s_pp

mC

u_pp

mD

y_pp

mE

r_pp

mE

u_pp

mFe

_ppm

Ga_

ppm

Gd_

ppm

Ge_

ppm

Hf_

ppm

Hg_

ppm

Ho_

ppm

I_pp

mIn

_ppm

K_p

pmLa

_ppm

Li_p

pmLu

_ppm

Mg_

ppm

Mn_

ppm

Mo_

ppm

Na_

ppm

Nb_

ppm

Nd_

ppm

Ni_

ppm

P_p

pmP

b_pp

mP

r_pp

mR

b_pp

mR

e_pp

mS

b_pp

mS

e_pp

mS

m_p

pmS

n_pp

mS

r_pp

mTa

_ppm

Tb_p

pmTe

_ppm

Th_p

pmTi

_ppm

Tl_p

pmTm

_ppm

U_p

pmV

_ppm

W_p

pmY

_ppm

Yb_

ppm

Zn_p

pm

Elements

% R

ecov

ery


Figure 4-3. Accuracy plot for two analyses of standard reference material LK4–ALG by cold hydroxylamine leach. RL is reporting limit.

Table 4-3. Summary statistics for assessing analytical variation on the Pebble project standard reference material PB–SMM; determined by a cold hydroxylamine hydrochloride leach of soil samples at ALS Chemex.

Element UnitsReporing



Ag ppm 0.002 8 0.016 0.026 0.002 6.29 163Al ppm 1.0 8 3,008 2,620 205 7.84 87.1As ppm 0.1 8 0.1 0.1 0 0 100Au ppm 0.05 8 0.05 <0.05 NA NA 90.2B ppm 2.0 8 2 <2 NA NA 90.6Ba ppm 0.05 8 63.6 61.1 2.61 4.28 96.1Be ppm 0.05 8 0.162 0.165 0.030 18 102Bi ppm 0.005 8 0.005 <0.005 NA NA 90.2Br ppm 2.0 8 2 3.1 1.15 37.2 155Ca ppm 10 8 1,540 1,490 34.8 2.34 96.7Cd ppm 0.01 8 0.024 0.023 0.005 20.6 93.8Ce ppm 0.005 8 5.094 4.96 0.175 3.53 97.3Co ppm 0.05 8 1.09 0.921 0.077 8.4 84.5Cr ppm 0.05 8 0.22 0.25 0.029 11.5 114Cs ppm 0.005 8 0.054 0.068 0.003 3.74 127Cu ppm 0.05 8 10.27 11 0.529 4.82 107Dy ppm 0.005 8 0.588 0.616 0.015 2.35 105


Table 4-3. Summary statistics for assessing analytical variation on the Pebble project standard reference material PB–SMM; determined by a cold hydroxylamine hydrochloride leach of soil samples at ALS Chemex.—Continued




Er ppm 0.005 8 0.296 0.31 0.005 1.58 105Eu ppm 0.005 8 0.153 0.17 0.005 2.84 111Fe ppm 5.0 8 405.8 391 40.7 10.4 96.3Ga ppm 0.05 8 0.142 0.161 0.018 11.2 114Gd ppm 0.005 8 0.684 0.725 0.014 1.95 106Ge ppm 0.1 8 0.1 <0.1 NA NA 91.1Hf ppm 0.01 8 0.032 0.029 0.004 12.3 89.8Hg ppm 0.1 8 0.1 <0.1 NA NA 91.1Ho ppm 0.005 8 0.120 0.117 0.004 3.3 97.3I ppm 0.1 8 1.06 1.4 0.12 8.54 132

In ppm 0.005 8 0.005 <0.005 NA NA 90.3K ppm 5.0 8 46.4 53.4 2.56 4.8 115La ppm 0.005 8 2.77 2.81 0.071 2.53 101Li ppm 0.05 8 0.06 0.051 0.009 17.8 85.5Lu ppm 0.005 8 0.033 0.033 0.002 5.69 101Mg ppm 1.0 8 148.4 143 7.77 5.43 96.4Mn ppm 0.1 8 72.66 66.3 6.06 9.14 91.3Mo ppm 0.01 8 0.01 0.013 0.005 37 125Na ppm 10 8 28 33.8 27.7 82.2 121Nb ppm 0.01 8 0.012 0.016 0.009 56.4 135Nd ppm 0.005 8 2.784 2.83 0.107 3.79 102Ni ppm 0.05 8 0.386 0.345 0.021 6 89.4P ppm 5.0 8 57.8 56.8 9.1 16 98.2

Pb ppm 0.1 8 0.5 0.538 0.074 13.8 108Pr ppm 0.005 8 0.705 0.692 0.033 4.77 98.2Rb ppm 0.01 8 0.616 0.719 0.024 3.36 117Re ppm 0.001 8 0.001 <0.001 NA NA 91.1Sb ppm 0.005 8 0.005 <0.005 NA NA 90.2Se ppm 0.5 8 0.5 <0.5 NA NA 90.2Sm ppm 0.005 8 0.532 0.585 0.015 2.57 110Sn ppm 0.05 8 0.05 <0.05 NA NA 90.2Sr ppm 0.05 8 14.44 13.5 0.252 1.87 93.4Ta ppm 0.01 8 0.01 <0.01 NA NA 91.1Tb ppm 0.005 8 0.107 0.109 0.002 2.18 101Te ppm 0.05 8 0.05 <0.05 NA NA 90.2Th ppm 0.01 8 0.03 0.021 0.008 39.3 70.8Ti ppm 1.0 8 5.4 6.13 1.36 22.1 113Tl ppm 0.005 8 0.016 0.016 0.001 4.72 103

Tm ppm 0.005 8 0.042 0.043 0.002 3.9 101U ppm 0.005 8 0.089 0.106 0.004 4.05 119V ppm 0.05 8 1.11 0.983 0.039 3.99 88.5


Table 4-3. Summary statistics for assessing analytical variation on the Pebble project standard reference material PB–SMM; determined by a cold hydroxylamine hydrochloride leach of soil samples at ALS Chemex.—Continued




W ppm 0.01 8 0.01 <0.01 NA NA 93.3Y ppm 0.005 8 3.622 3.63 0.092 2.53 100

Yb ppm 0.005 8 0.212 0.228 0.005 1.98 107Zn ppm 0.2 8 0.72 0.7 0.076 10.8 97.2Zr ppm 0.05 8 0.678 0.784 0.089 11.4 116


based on Standard Reference Material PB-SMM

0

10

20

30

40

50

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70

80

90

Ag_

ppm

Al_

ppm

As_

ppm

Au_

ppm

B_p

pmB

a_pp

mB

e_pp

mB

i_pp

mB

r_pp

mC

a_pp

mC

d_pp

mC

e_pp

mC

o_pp

mC

r_pp

mC

s_pp

mC

u_pp

mD

y_pp

mE

r_pp

mE

u_pp

mFe

_ppm

Ga_

ppm

Gd_

ppm

Ge_

ppm

Hf_

ppm

Hg_

ppm

Ho_

ppm

I_pp

mIn

_ppm

K_p

pmLa

_ppm

Li_p

pmLu

_ppm

Mg_

ppm

Mn_

ppm

Mo_

ppm

Na_

ppm

Nb_

ppm

Nd_

ppm

Ni_

ppm

P_p

pmP

b_pp

mP

r_pp

mR

b_pp

mR

e_pp

mS

b_pp

mS

e_pp

mS

m_p

pmS

n_pp

mS

r_pp

mTa

_ppm

Tb_p

pmTe

_ppm

Th_p

pmTi

_ppm

Tl_p

pmTm

_ppm

U_p

pmV

_ppm

W_p

pmY

_ppm

Yb_

ppm

Zn_p

pmZr

_ppm

Elements

% R

SD


Figure 4-4. Precision plot for eight analyses of Pebble project standard reference material PB–SMM by cold hydroxylamine leach. %RSD is percent relative standard deviation; RL is reporting limit.


Analysis of Analytical AccuracyCold Hydroxylamine Hydrochloride Leach of Soils (ALS Chemex)


0

20

40

60

80

100

120

140

160

180A

g_pp

mA

l_pp

mA

s_pp

mA

u_pp

mB

_ppm

Ba_

ppm

Be_

ppm

Bi_

ppm

Br_

ppm

Ca_

ppm

Cd_

ppm

Ce_

ppm

Co_

ppm

Cr_

ppm

Cs_

ppm

Cu_

ppm

Dy_

ppm

Er_

ppm

Eu_

ppm

Fe_p

pmG

a_pp

mG

d_pp

mG

e_pp

mH

f_pp

mH

g_pp

mH

o_pp

mI_

ppm

In_p

pmK

_ppm

La_p

pmLi

_ppm

Lu_p

pmM

g_pp

mM

n_pp

mM

o_pp

mN

a_pp

mN

b_pp

mN

d_pp

mN

i_pp

mP

_ppm

Pb_

ppm

Pr_

ppm

Rb_

ppm

Re_

ppm

Sb_

ppm

Se_

ppm

Sm

_ppm

Sn_

ppm

Sr_

ppm

Ta_p

pmTb

_ppm

Te_p

pmTh

_ppm

Ti_p

pmTl

_ppm

Tm_p

pmU

_ppm

V_p

pmW

_ppm

Y_p

pmY

b_pp

mZn

_ppm

Elements

% R

ecov

ery

Mean >5 x LDLMean <5 x LDL85% Recovery115% Recovery

Figure 4-5. Accuracy plot for eight analyses of standard reference material PB–SMM by cold hydroxylamine leach. RL is reporting limit.

Appendix 5: Quality Control Tables and Charts for ALS Chemex Ionic Leach Data

Table 5-1. Summary statistics for assessing analytical variation on the standard reference material ION–SRM18; determined by an ionic leach of soil samples at ALS Chemex.—Continued




Ag ppb 0.1 7 17.55 18.5 1.13 6.13 105As ppb 2.0 7 8 6.86 1.07 15.6 85.7Au ppb 0.02 7 7.61 7.37 0.47 6.37 96.9Ba ppb 10 7 210 217 26.9 12.4 103Be ppb 0.2 7 0.3 0.249 0.103 41.5 83Bi ppb 3.0 7 3 <3 NA NA 90.4Br ppb 0.05 7 1.42 1.53 0.048 3.16 107Ca ppm 0.2 7 155.25 149 9.19 6.18 95.7Cd ppb 1.0 7 65.5 64.4 4.24 6.58 98.4Ce ppb 0.1 7 15.2 15 1.02 6.82 98.8Co ppb 0.3 7 60.95 62 2.97 4.8 102Cr ppb 1.0 7 5.5 5.43 1.13 20.9 98.7Cs ppb 0.1 7 7.4 7.8 0.342 4.38 105Cu ppb 1 7 771 754 38.3 5.07 97.8Dy ppb 0.1 7 1.1 1.24 0.054 4.3 113Er ppb 0.1 7 0.7 0.714 0.107 15 102

Appendix 5: Quality Control Tables and Charts for ALS Chemex Ionic Leach Data 55

Table 5-1. Summary statistics for assessing analytical variation on the standard reference material ION–SRM18; determined by an ionic leach of soil samples at ALS Chemex.—Continued




Eu ppb 0.1 7 0.8 0.786 0.121 15.5 98.2Fe ppm 0.1 7 2.35 2.2 0.258 11.7 93.6Ga ppb 0.5 7 5.65 6.1 0.416 6.83 108Gd ppb 0.1 7 2.65 2.66 0.223 8.38 100Ge ppb 0.1 7 0.1 <0.1 NA NA 93.7Hf ppb 0.5 7 0.6 <0.5 NA NA 79.9Hg ppb 0.1 7 4.25 4.01 0.291 7.25 94.5Ho ppb 0.1 7 0.1 0.157 0.054 34 157I ppm 0.01 7 0.15 0.149 0.016 10.6 99

In ppb 0.1 7 0.15 <0.1 NA NA 60.7La ppb 0.1 7 5 5.1 0.2 3.92 102Li ppb 0.2 7 0.4 0.457 0.14 30.6 114Lu ppb 0.1 7 0.1 <0.1 NA NA 96.2Mg ppm 0.01 7 73.8 71.9 3.6 5.0 97.5Mn ppm 0.01 7 0.47 0.464 0.031 6.56 98.8Mo ppb 0.5 7 29.8 30.4 1.61 5.31 102Nb ppb 0.1 7 0.1 <0.1 NA NA 91.1Nd ppb 0.1 7 12.8 12 0.283 2.36 93.8Ni ppb 1.0 7 551 553 37.5 6.77 100Pb ppb 1.0 7 87 83.6 7.14 8.54 96.1Pd ppb 0.1 7 11.9 12.1 0.608 5.01 102Pr ppb 0.1 7 2 2 0.115 5.77 100Rb ppb 0.1 7 174 178 9.04 5.08 102Re ppb 0.1 7 0.1 <0.1 NA NA 91.1Sb ppb 0.5 7 0.55 <0.5 NA NA 82Se ppb 2.0 7 17 14.6 1.13 7.78 85.7Sm ppb 0.1 7 2.9 2.79 0.121 4.36 96.1Sn ppb 0.2 7 0.2 <0.2 NA NA 91.9Sr ppb 1.0 7 1,122 1,110 60 5.42 98.5Ta ppb 1.0 7 1.5 <1 NA NA 60.7Tb ppb 0.1 7 0.4 0.414 0.107 25.8 104Te ppb 1 7 1 <1 NA NA 91.1Th ppb 0.02 7 3.48 3.64 0.166 4.55 105Ti ppb 5.0 7 39 31.1 0.69 2.22 79.9Tl ppb 0.5 7 0.55 <0.5 NA NA 82

Tm ppb 0.1 7 0.1 0.112 0.039 35 112U ppb 0.1 7 9.75 9.54 0.559 5.86 97.9W ppb 1.0 7 1 <1 NA NA 91.1Y ppb 0.1 7 9.15 9.06 0.391 4.32 99

Yb ppb 0.1 7 0.3 0.343 0.054 15.6 114Zn ppb 10 7 600 557 19.8 3.55 92.9Zr ppb 0.1 7 4.7 5.04 0.257 5.1 107


Analysis of Analytical PrecisionIonic Leach of Soils (ALS Chemex)

based on Standard Reference Material ION-SRM18

0

5

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Ag_

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As_

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ppb

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Cu_

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Er_

ppb

Eu_

ppb

Fe_p

pmG

a_pp

bG

d_pp

bG

e_pp

bH

f_pp

bH

g_pp

bH

o_pp

bI_

ppm

In_p

pbLa

_ppb

Li_p

pbLu

_ppb

Mg_

ppM

n_pp

mM

o_pp

bN

b_pp

bN

d_pp

bN

i_pp

bP

b_pp

bP

d_pp

bP

r_pp

bR

b_pp

bR

e_pp

bS

b_pp

bS

e_pp

bS

m_p

pbS

n_pp

bS

r_pp

bTa

_ppb

Tb_p

pbTe

_ppb

Th_p

pbTi

_ppb

Tl_p

pbTm

_ppb

U_p

pbW

_ppb

Y_p

pbY

b_pp

bZn

_ppb

Zr_p

pb

Elements

% R

SD


Figure 5-1. Precision plot for seven analyses of standard reference material ION–SRM18 by ionic leach. %RSD is percent relative standard deviation; RL is reporting limit.

Table 5-2. Summary statistics for assessing analytical variation on the standard reference material SAR–L; determined by an ionic leach of soil samples at ALS Chemex.—Continued

Element Units RL nTarget Value Mean


Ag ppb 0.1 4 NA 656 54.5 8.31 NAAs ppb 2.0 4 NA 15 1.41 9.43 NAAu ppb 0.02 4 NA 47.4 10.1 21.2 NABa ppb 10 4 NA 1,650 319 19.3 NABe ppb 0.2 4 NA 1.03 0.096 9.34 NABi ppb 3.0 4 NA <3 NA NA NABr ppb 0.05 4 NA 0.22 0.072 32.6 NACa ppm 0.2 4 NA 405 26.2 6.47 NACd ppb 1.0 4 NA 266 45.5 17.1 NACe ppb 0.1 4 NA 141 43.7 31.1 NACo ppb 0.3 4 NA 79.1 9.48 12 NACr ppb 1.0 4 NA 9 3.16 35.1 NACs ppb 0.1 4 NA 36.3 3.6 9.91 NACu ppb 1.0 4 NA 22,800 1,500 6.57 NADy ppb 0.1 4 NA 22.5 8.39 37.3 NAEr ppb 0.1 4 NA 14.6 1.76 12 NAEu ppb 0.1 4 NA 4.05 0.238 5.88 NAFe ppm 0.1 4 NA 15.4 4.03 26.1 NAGa ppb 0.5 4 NA 64.3 18.2 28.3 NA


Table 5-2. Summary statistics for assessing analytical variation on the standard reference material SAR–L; determined by an ionic leach of soil samples at ALS Chemex.—Continued



Gd ppb 0.1 4 NA 34.9 6.27 18 NAGe ppb 0.1 4 NA 0.4 0 0 NAHf ppb 0.5 4 NA 0.501 0.070 14 NAHg ppb 0.1 4 NA 4.25 0.686 16.1 NAHo ppb 0.1 4 NA 4.98 1.19 23.9 NAI ppm 0.01 4 NA 0.108 0.021 19.2 NA

In ppb 0.1 4 NA <0.1 NA NA NALa ppb 0.1 4 NA 81.8 2.75 3.36 NALi ppb 0.2 4 NA 7.55 1.08 14.3 NALu ppb 0.1 4 NA 1.78 0.33 18.6 NAMg ppm 0.01 4 NA 70.7 2.81 3.98 NAMn ppm 0.01 4 NA 18.2 4.16 22.8 NAMo ppb 0.5 4 NA 1,180 71.2 6.05 NANb ppb 0.1 4 NA 0.425 0.096 22.5 NANd ppb 0.1 4 NA 125 11.5 9.19 NANi ppb 1.0 4 NA 281 14 4.97 NAPb ppb 1.0 4 NA 6,490 420 6.47 NAPd ppb 0.1 4 NA 1.13 0.907 80.6 NAPr ppb 0.1 4 NA 24.9 4.51 18.1 NARb ppb 0.1 4 NA 401 26.5 6.61 NARe ppb 0.1 4 NA 0.1 0 0 NASb ppb 0.5 4 NA 17 6.44 37.8 NASe ppb 2.0 4 NA 24.5 1.91 7.82 NASm ppb 0.1 4 NA 29.8 4.81 16.1 NASn ppb 0.2 4 NA 0.225 0.05 22.2 NASr ppb 1.0 4 NA 2,240 42.4 1.89 NATa ppb 1.0 4 NA <1 NA NA NATb ppb 0.1 4 NA 5.23 0.562 10.8 NATe ppb 1.0 4 NA <1 NA NA NATh ppb 0.02 4 NA 20 3.05 15.2 NATi ppb 5.0 4 NA 25.5 9.57 37.5 NATl ppb 0.5 4 NA 1.58 0.479 30.4 NA

Tm ppb 0.1 4 NA 1.85 0.37 20 NAU ppb 0.1 4 NA 66.2 8.08 12.2 NAW ppb 1.0 4 NA 2 0 0 NAY ppb 0.1 4 NA 128 6.98 5.44 NA

Yb ppb 0.1 4 NA 10.6 1.58 14.9 NAZn ppb 10 4 NA 5,130 319 6.22 NAZr ppb 0.1 4 NA 7.38 2.51 34.1 NA



based on Standard Reference Material SAR-L

0

10

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Ag_

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Ba_

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ppb

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ppb

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ppb

Fe_p

pmG

a_pp

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d_pp

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e_pp

bH

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g_pp

bH

o_pp

bI_

ppm

In_p

pbLa

_ppb

Li_p

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n_pp

mM

o_pp

bN

b_pp

bN

d_pp

bN

i_pp

bP

b_pp

bP

d_pp

bP

r_pp

bR

b_pp

bR

e_pp

bS

b_pp

bS

e_pp

bS

m_p

pbS

n_pp

bS

r_pp

bTa

_ppb

Tb_p

pbTe

_ppb

Th_p

pbTi

_ppb

Tl_p

pbTm

_ppb

U_p

pbW

_ppb

Y_p

pbY

b_pp

bZn

_ppb

Zr_p

pb

Elements

% R

SD


Figure 5-3. Precision plot for four analyses of standard reference material SAR–L by ionic leach. %RSD is percent relative standard deviation; RL is reporting limit.

Analysis of Analytical AccuracyIonic Leach of Soils (ALS Chemex)

based on Standard Reference Material ION-SRM18

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bH

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bI_

ppm

In_p

pbLa

_ppb

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pbLu

_ppb

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ppM

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mM

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bP

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bP

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bR

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bR

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bS

e_pp

bS

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pbS

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bS

r_pp

bTa

_ppb

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pbTe

_ppb

Th_p

pbTi

_ppb

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pbTm

_ppb

U_p

pbW

_ppb

Y_p

pbY

b_pp

bZn

_ppb

Zr_p

pb

Elements

% R

ecov

ery


Figure 5-2. Accuracy plot for seven analyses of standard reference material ION-SRM18 by ionic leach. RL is reporting limit.


Table 5-3. Summary statistics for assessing analytical variation on the standard reference material PB–SMM; determined by an ionic leach of soil samples at ALS Chemex.—Continued



Ag ppb 0.1 14 NA 5.96 2.45 41.2 NAAs ppb 2.0 14 NA 7.21 2.46 34 NAAu ppb 0.02 14 NA 3.75 0.519 13.9 NABa ppb 10 14 NA 3,050 829 27.2 NABe ppb 0.2 14 NA 7.77 0.997 12.8 NABi ppb 3.0 14 NA <3 NA NA NABr ppb 0.05 14 NA 0.356 0.065 18.1 NACa ppm 0.2 14 NA 188 29.9 15.9 NACd ppb 1.0 14 NA 7.07 1.59 22.5 NACe ppb 0.1 14 NA 164 72.1 43.9 NACo ppb 0.3 14 NA 54.3 8.98 16.5 NACr ppb 1.0 14 NA 7.79 3.83 49.1 NACs ppb 0.1 14 NA 18.3 2 10.9 NACu ppb 1.0 14 NA 2,730 323 11.8 NADy ppb 0.1 14 NA 118 19.3 16.3 NAEr ppb 0.1 14 NA 106 14.7 13.9 NAEu ppb 0.1 14 NA 22.7 2.88 12.7 NAFe ppm 0.1 14 NA 65.6 16 24.3 NAGa ppb 0.5 14 NA 120 39.7 33.1 NAGd ppb 0.1 14 NA 87.1 9.13 10.5 NAGe ppb 0.1 14 NA 0.679 0.172 25.3 NAHf ppb 0.5 14 NA 2.96 0.352 11.9 NAHg ppb 0.1 14 NA 0.192 0.16 83 NAHo ppb 0.1 14 NA 32.4 4.64 14.3 NAI ppb 0.01 14 NA 0.186 0.034 18.4 NA

In ppb 0.1 14 NA 0.192 0.084 43.5 NALa ppb 0.1 14 NA 88.7 23.5 26.5 NALi ppb 0.2 14 NA 0.294 0.259 88.1 NALu ppb 0.1 14 NA 13.3 1.86 14 NAMg ppm 0.01 14 NA 48.3 8.21 17 NAMn ppm 0.01 14 NA 3.85 0.547 14.2 NAMo ppb 0.5 14 NA 3.84 1.59 41.4 NANb ppb 0.1 14 NA 0.414 0.095 22.9 NANd ppb 0.1 14 NA 220 44.6 20.3 NANi ppb 1.0 14 NA 63.7 10.3 16.2 NAPb ppb 1.0 14 NA 111 36.7 33 NAPd ppb 0.1 14 NA 6.24 2.04 32.7 NAPr ppb 0.1 14 NA 40.3 7.12 17.7 NARb ppb 0.1 14 NA 193 15.3 7.93 NARe ppb 0.1 14 NA 0.1 0 0 NASb ppb 0.5 14 NA <0.5 NA NA NA


Table 5-3. Summary statistics for assessing analytical variation on the standard reference material PB–SMM; determined by an ionic leach of soil samples at ALS Chemex.—Continued



Se ppb 2.0 14 NA 21.6 5.96 27.6 NASm ppb 0.1 14 NA 63.7 9.62 15.1 NASn ppb 0.2 14 NA <0.2 NA NA NASr ppb 1.0 14 NA 2,390 473 19.8 NATa ppb 1.0 14 NA <1 NA NA NATb ppb 0.1 14 NA 21.4 1.97 9.2 NATe ppb 1.0 14 NA <1 NA NA NATh ppb 0.02 14 NA 10.3 2.14 20.7 NATi ppb 5.0 14 NA 139 40.9 29.4 NATl ppb 0.5 14 NA 1.97 0.31 15.7 NA

Tm ppb 0.1 14 NA 14.5 1.8 12.4 NAU ppb 0.1 14 NA 41.4 10.9 26.3 NAW ppb 1.0 14 NA <1 NA NA NAY ppb 0.1 14 NA 706 114 16.1 NAYb ppb 0.1 14 NA 85.6 11.9 13.9 NAZn ppb 10 14 NA 142 18.5 13 NAZr ppb 0.1 14 NA 62.7 17.7 28.2 NA



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ppb

As_

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ppm

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ppb

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pbLa

_ppb

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_ppb

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ppM

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mM

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_ppb

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pbTe

_ppb

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_ppb

Tl_p

pbTm

_ppb

U_p

pbW

_ppb

Y_p

pbY

b_pp

bZn

_ppb

Zr_p

pb

Elements

% R

SD


Figure 5-4. Precision plot for 14 analyses of standard reference material PB–SMM by ionic leach. %RSD is percent relative standard deviation; RL is reporting limit.

Appendix 6: Quality Control Tables and Charts for SGS Mineral Service 61

Appendix 6: Quality Control Tables and Charts for SGS Mineral Service (USGS contract) Data: ICPAES–MS42 Multielement Package, ICPAES–MS55 Multielement Package, Forms of Carbon, and Selected Single Element Methods

Table 6-1. Summary statistics for assessing analytical variation on duplicate samples; determined by a four-acid total digestion of soil samples by the ICPAES–MS42 multielement package at SGS Minerals.—Continued




Ag ppm 1.0 2 3 4 3.75 0.5 13.3Al % 0.01 11 5.5 8.63 7.14 0.342 4.79As ppm 1.0 11 6 39 14.3 1.07 7.45Ba ppm 5.0 11 573 811 695 22.6 3.26Be ppm 0.1 11 0.7 2.6 1.42 0.1 7.05Bi ppm 0.04 11 0.1 1.78 0.425 0.050 11.8Ca % 0.01 11 0.49 2.69 1.49 0.070 4.72Cd ppm 0.1 3 0.1 5.4 3.42 0.204 5.97Ce ppm 0.05 11 28.8 113 52.8 1.34 2.55Co ppm 0.1 11 6.7 17.3 11.5 0.354 3.09Cr ppm 1.0 11 25 91 53.4 4.21 7.89Cs ppm 5.0 1 5 5 5 0 0Cu ppm 0.5 11 9.2 534 125 7.11 5.68Fe % 0.01 11 2.88 5.94 3.94 0.152 3.87Ga ppm 0.05 11 12 19.2 16.2 0.411 2.53In ppm 0.02 11 0.04 1.13 0.234 0.032 13.6K % 0.01 11 1.08 2.64 1.55 0.083 5.36La ppm 0.5 11 13.8 54.7 25.6 0.942 3.69Li ppm 1.0 11 12 27 18.8 1.07 5.68

Mg % 0.01 11 0.44 0.99 0.715 0.031 4.28Mn ppm 5.0 11 398 5,210 1,450 124 8.55Mo ppm 0.05 11 0.71 13.9 3.67 0.39 10.6Na % 0.01 11 1.06 2.52 1.79 0.081 4.52Nb ppm 0.1 11 7.6 33.1 13.5 1.62 12Ni ppm 0.5 11 8 38.2 17.5 0.65 3.72P ppm 50 11 580 1,230 845 39.7 4.7

Pb ppm 0.5 11 8.9 929 170 4.5 2.65Rb ppm 0.2 11 37.3 151 61.9 3.77 6.1S % 0.01 11 0.01 0.13 0.057 0.006 9.93Sb ppm 0.05 11 0.9 6.68 2.03 0.146 7.19Sc ppm 0.1 11 7 16.9 12.6 0.445 3.54Sn ppm 0.1 11 1.1 3.7 1.76 0.215 12.2Sr ppm 0.5 11 130 342 242 11.8 4.89Te ppm 0.1 2 0.8 1 0.9 0.071 7.86Th ppm 0.2 11 3.5 16.7 6.37 0.383 6.02


Table 6-1. Summary statistics for assessing analytical variation on duplicate samples; determined by a four-acid total digestion of soil samples by the ICPAES–MS42 multielement package at SGS Minerals.—Continued




Ti % 0.01 11 0.23 0.9 0.459 0.033 7.13Tl ppm 0.1 11 0.3 2.6 0.745 0.043 5.72U ppm 0.1 11 1.3 3.5 2 0.135 6.74V ppm 1.0 11 62 208 110 6.64 6.03W ppm 0.1 11 0.5 9.3 2.2 0.133 6.06Y ppm 0.1 11 13.3 26.2 19.3 0.418 2.17Zn ppm 1.0 11 49 957 211 17.2 8.16

0

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_ppm

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_ppm

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_ppm

Th_p

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_%Tl

_ppm

U_p

pmV_

ppm

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pmY_

ppm

Zn_p

pm

Elements

% R

SD

Mean >5 x RL

Mean <5 x RL

Below RL

Control Limit

Analysis of Analytical PrecisionICPAES-MS42 Total Analysis of Soils (SGS Mineral Services)


Figure 6-1. Precision plot for 11 analytical duplicate sample pairs by ICPAES–MS42. %RSD is percent relative standard deviation; RL is reporting limit.

Appendix 6: Quality Control Tables and Charts for SGS Mineral Service Data 63

Table 6-2. Summary statistics for assessing analytical variation on duplicate samples; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals.—Continued




Ag ppm 1.0 2 1 5 2.75 0.5 18.2Al % 0.01 10 5.64 8.16 7.74 0.325 4.21As ppm 30 2 30 40 35 0 0Ba ppm 0.5 10 614 872 756 34.8 4.61Be ppm 5.0 1 7 7 7 0 0Bi ppm 0.1 7 0.1 1.5 0.521 0.071 13.6Ca % 0.01 10 0.52 2.85 1.49 0.072 4.84Cd ppm 0.2 2 3.9 4.9 4.53 0.304 6.72Ce ppm 0.1 10 29 119 57.5 3.33 5.8Co ppm 0.5 10 6.7 16.1 11.6 0.496 4.28Cr ppm 10 10 30 170 84.5 7.42 8.78Cs ppm 0.1 10 1.9 4.9 2.95 0.022 0.759Cu ppm 5.0 10 12 584 153 21.4 13.9Dy ppm 0.05 10 2.86 7.61 4.58 0.231 5.04Er ppm 0.05 10 1.9 4.37 2.75 0.096 3.49Eu ppm 0.05 10 0.84 1.44 1.15 0.054 4.75Fe % 0.01 10 3.07 7.2 4.25 0.237 5.59Ga ppm 1.0 10 16 22 18.2 1.1 6.02Gd ppm 0.05 10 3.21 7.89 4.98 0.161 3.23Ge ppm 1.0 10 1 2 1.45 0.224 15.4Hf ppm 1.0 10 4 22 8.15 0.975 12Ho ppm 0.05 10 0.6 1.57 0.928 0.035 3.76In ppm 0.2 2 0.8 1.1 0.925 0.112 12.1K % 0.01 10 1.19 2.95 1.63 0.044 2.7La ppm 0.1 10 13.3 61 28.2 1.4 4.97Li ppm 10 10 10 50 21.5 7.42 34.5Lu ppm 0.05 10 0.28 0.72 0.434 0.044 10.2Mg % 0.01 10 0.47 1.09 0.752 0.021 2.74Mn % 0.01 10 0.04 0.5 0.158 0.007 4.48Mo ppm 2.0 2 11 13 12.3 1.12 9.13Nb ppm 1.0 10 8 37 16.7 0.548 3.28Nd ppm 0.1 10 13.4 49.6 25.7 1.02 3.96Ni ppm 5.0 9 17 108 46.7 0 0P % 0.01 10 0.06 0.15 0.094 0.007 7.17

Pb ppm 5.0 10 10 930 185 10 5.4Pr ppm 0.05 10 3.19 13.3 6.52 0.286 4.39Rb ppm 0.2 10 37.4 153 66.4 1.43 2.16Sb ppm 0.1 10 0.8 6.7 2.11 0.095 4.5Sc ppm 5.0 10 5 19 12.1 1.55 12.8Sm ppm 0.1 10 3.2 9.5 5.19 0.249 4.8


Table 6-2. Summary statistics for assessing analytical variation on duplicate samples; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals.—Continued




Sn ppm 1.0 10 1 5 2.5 0.632 25.3Sr ppm 0.1 10 152 351 250 5.05 2.02Ta ppm 0.5 7 0.6 2 1.07 0.355 33.1Tb ppm 0.1 10 0.51 1.35 0.773 0.028 3.6Th ppm 0.1 10 3.9 18.5 7.34 0.297 4.06Ti % 0.01 10 0.35 1.27 0.57 0.039 6.77Tl ppm 0.01 2 2.2 2.6 2.43 0.112 4.61

Tm ppm 0.05 10 0.28 0.73 0.408 0.031 7.55U ppm 0.05 10 1.78 4.39 2.51 0.115 4.57V ppm 5.0 10 67 264 124 8.76 7.06W ppm 1.0 4 1 9 4.88 0.612 12.6Y ppm 0.5 10 16.5 37.9 24.7 0.602 2.44

Yb ppm 0.1 10 2 4.7 2.79 0.179 6.41Zn ppm 5.0 10 48 886 225 9.76 4.34Zr ppm 0.5 10 170 871 302 9.29 3.08

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pm

Elements

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SD

Mean >5 x RL

Mean <5 x RL

Below RL

Control Limit

Analysis of Analytical PrecisionICPAES-MS55 Total Analysis of Soils (SGS Mineral Services)


Figure 6-2. Precision plot for ten analytical duplicate sample pairs by ICPAES–MS55. %RSD is percent relative standard deviation; RL is reporting limit.


Table 6-3. Summary statistics for assessing analytical variation on duplicate samples; determined by single-element methods at SGS Minerals.




Sb_Hyd ppm 0.6 11 0.6 6.6 1.68 0.117 6.94Se_Hyd ppm 0.2 8 0.3 1.2 0.613 0.05 8.16

Hg_CVAA ppm 0.01 6 0.02 0.23 0.088 0.005 5.71Au_FA ppm 0.01 1 0.244 0.302 0.273 0.041 15Cl_ISE ppm 50 11 70 310 171 10.7 6.22F_ISE ppm 20 11 190 850 366 11.1 3.03CO2 % 0.01 10 0.02 0.3 0.100 0.024 24.5

Tot C % 0.01 11 0.33 4.97 2.18 0.016 0.744

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Mean <5 x RL

Below RL

Control Limit

Analysis of Analytical PrecisionMiscellanenous Methods Analysis of Soils (SGS Mineral Services)


Figure 6-3. Precision plot for 11 analytical duplicate sample pairs by single-element methods. %RSD is percent relative standard deviation; RL is reporting limit.


Table 6-4. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–L; determined after a four-acid total digestion of soil samples by the ICPAES–MS42 multielement package at SGS Minerals.




Ag ppm 1.0 7 2.56 3.57 0.787 22 140Al % 0.01 7 5.79 5.72 0.226 3.94 98.8As ppm 1.0 7 16.5 17.1 0.9 5.25 104Ba ppm 5.0 7 879.2 882 56.7 6.43 100Be ppm 0.1 7 3.24 3.86 0.94 24.4 119Bi ppm 0.04 7 1.1 1.16 0.101 8.71 105Ca % 0.01 7 1.06 1.03 0.075 7.28 97.4Cd ppm 0.1 7 2.5 3 0.115 3.85 120Ce ppm 0.05 7 150 149 10.5 7.07 99.4Co ppm 0.1 7 7.5 7.69 0.53 6.9 102Cr ppm 1.0 7 110 93.9 6.01 6.41 85.3Cs ppm 5.0 7 5 <5 NA NA 100Cu ppm 0.5 7 370 351 20.5 5.84 95Fe % 0.01 7 2.67 2.66 0.1 3.77 99.5Ga ppm 0.05 7 17 16.2 2 12.4 95.5In ppm 0.02 7 0.26 0.29 0.01 3.45 112K % 0.01 7 2.98 2.82 0.189 6.72 94.5La ppm 0.5 7 75 69.1 2.64 3.82 92.1Li ppm 1.0 7 28 26.4 0.976 3.69 94.4

Mg % 0.01 7 0.55 0.511 0.030 5.8 93Mn ppm 5.0 7 2,094 2,100 105 5.02 100Mo ppm 0.05 7 13 14 1.14 8.17 107Na % 0.01 7 1.53 1.48 0.072 4.85 96.5Nb ppm 0.1 7 35 32.3 2.57 7.96 92.4Ni ppm 0.5 7 52 47.5 3.43 7.21 91.3P ppm 50 7 900 733 19.8 2.7 81.4

Pb ppm 0.5 7 578 561 44.2 7.87 97.1Rb ppm 0.2 7 140 143 4.96 3.48 102S % 0.01 7 0.07 0.073 0.008 10.4 104Sb ppm 0.05 7 5.1 5.32 0.197 3.7 104Sc ppm 0.1 7 7.8 7.64 0.58 7.59 98Sn ppm 0.1 7 6 4.43 0.709 16 73.8Sr ppm 0.5 7 158 148 6.7 4.54 93.4Te ppm 0.1 7 0.6 0.686 0.318 46.4 114Th ppm 0.2 7 19 19.7 1.38 7.03 104Ti % 0.01 7 0.25 0.213 0.010 4.47 85.1Tl ppm 0.1 7 1.4 1.33 0.125 9.44 94.9U ppm 0.1 7 5.2 4.26 0.19 4.47 81.9V ppm 1.0 7 140 135 9.56 7.09 96.3W ppm 0.1 7 3.7 3.17 0.111 3.51 85.7Y ppm 0.1 7 44 36.7 2.69 7.33 83.4Zn ppm 1.0 7 420 432 21.1 4.88 103


Analysis of Analytical PrecisionICPAES-MS42 Total Analysis of Soils, Sediments, and Core (SGS Mineral Services)


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_ppm

Elements

% R

SD


Figure 6-4. Precision plot for seven analyses of USGS standard reference material SAR–L by ICPAES–MS42. %RSD is percent relative standard deviation; RL is reporting limit.

Analysis of Analytical AccuracyICPAES-MS42 Total Analysis of Soils, Sediments, and Core (SGS Mineral Services)


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_ppm

Elements

% R

ecov

ery


Figure 6-5. Accuracy plot for seven analyses of USGS standard reference material SAR–L by ICPAES–MS42. RL is reporting limit.


Table 6-5. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–L; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals.—Contiued




Ag ppm 1.0 7 2.56 3 0 0 117Al % 0.01 7 5.79 6.09 0.207 3.41 105As ppm 30 7 30 <30 NA NA 100Ba ppm 0.5 7 879.2 930 79.8 8.58 106Be ppm 5.0 7 5 5.72 2.01 35.2 127Bi ppm 0.1 7 1.1 1.2 0.058 4.81 109Ca % 0.01 7 1.06 1.03 0.060 5.83 97.3Cd ppm 0.2 7 2.5 2.76 0.113 4.11 110Ce ppm 0.1 7 150 147 6.13 4.18 97.7Co ppm 0.5 7 7.5 7.3 0.356 4.88 97.3Cr ppm 10 7 110 106 9.76 9.23 96.1Cs ppm 0.1 7 4 4.2 0.351 8.36 105Cu ppm 5.0 7 370 358 31.1 8.68 96.8Dy ppm 0.05 7 NA 10.5 0.72 6.82 NAEr ppm 0.05 7 NA 6.66 0.356 5.34 NAEu ppm 0.05 7 1.5 1.39 0.071 5.13 92.4Fe % 0.01 7 2.67 2.69 0.076 2.82 101Ga ppm 1.0 7 17 17.6 1.62 9.21 103Gd ppm 0.05 7 NA 11.1 0.61 5.48 NAGe ppm 1.0 7 NA 1.57 0.535 34 NAHf ppm 1.0 7 10 10.4 0.787 7.54 104Ho ppm 0.05 7 1.9 2.16 0.055 2.54 114In ppm 0.2 7 0.26 0.286 0.038 13.2 110K % 0.01 7 2.98 2.86 0.138 4.83 96La ppm 0.1 7 75 69.7 3.54 5.08 92.9Li ppm 10 7 28 27.1 15 55.1 96.9Lu ppm 0.05 7 1 0.94 0.046 4.91 94Mg % 0.01 7 0.55 0.506 0.021 4.09 91.9Mn % 0.001 7 0.209 0.214 0.005 2.49 103Mo ppm 2.0 7 13 13.4 0.787 5.86 103Nb ppm 1.0 7 35 37.9 2.79 7.38 108Nd ppm 0.1 7 66 59.7 2.07 3.46 90.5Ni ppm 5.0 7 52 66.9 25 37.4 129P % 0.01 7 0.09 0.079 0.007 8.78 87.3

Pb ppm 5.0 7 578 590 21 3.56 102Pr ppm 0.05 7 NA 16 0.793 4.96 NARb ppm 0.2 7 140 146 5.4 3.69 104Sb ppm 0.1 7 5.1 5.07 0.18 3.55 99.4Sc ppm 5.0 7 7.8 7.14 1.95 27.3 91.6Sm ppm 0.1 7 13 11.3 0.359 3.19 86.7


Table 6-5. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–L; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals.—Contiued




Sn ppm 1.0 7 6 5.57 0.787 14.1 92.9Sr ppm 0.1 7 158 149 6.92 4.63 94.6Ta ppm 0.5 7 2.8 2.04 0.151 7.4 73Tb ppm 0.05 7 1.7 1.75 0.080 4.58 103Th ppm 0.1 7 19 18.9 1.39 7.37 99.2Ti % 0.01 7 0.25 0.299 0.014 4.51 119Tl ppm 0.5 7 1.4 1.23 0.049 3.97 87.8

Tm ppm 0.05 7 NA 0.937 0.041 4.34 NAU ppm 0.05 7 5.2 4.5 0.242 5.37 86.5V ppm 5.0 7 140 136 5.18 3.81 97W ppm 1.0 7 3.7 3.71 0.488 13.1 100Y ppm 0.5 7 44 57.7 2.21 3.83 131

Yb ppm 0.1 7 5.7 6.33 0.298 4.72 111Zn ppm 5.0 7 420 456 27.4 6 109Zr ppm 0.5 7 408 359 31.8 8.86 88.1

Analysis of Analytical PrecisionICPAES-MS55 Total Analysis of Soils, Sediments, And Cores (SGS Mineral Services)


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Figure 6-6. Precision plot for seven analyses of USGS standard reference material SAR–L by ICPAES–MS55. %RSD is percent relative standard deviation; RL is reporting limit.


Analysis of Analytical AccuracyICPAES-MS55 Total Analysis of Soils, Sediments, and Cores (SGS Mineral Services)


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ery

Mean >5 x RLMean <5 x RLNo Target Value85% Recovery115% Recovery

Figure 6-7. Accuracy plot for seven analyses of USGS standard reference material SAR–L by ICPAES–MS55. RL is reporting limit.

Table 6-6. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–L; determined by various methods at SGS Minerals.





Hg_CVAA ppm 0.02 4 0.155 0.175 0.006 3.3 113Au_FA ppm 0.005 6 0.325 0.511 0.274 53.7 157Cl_ISE ppm 50 7 137 146 5.35 3.67 106F_ISE ppm 20 7 947 874 25.1 2.87 92.3CO2 % 0.01 7 0.4 0.38 0.008 2.15 95

Carb CO2 % 0.003 7 0.11 0.103 0.005 4.74 93.5Org C % 0.05 7 0.86 1.01 0.018 1.76 117Tot C % 0.01 7 0.97 1.11 0.018 1.6 115


Analysis of Analytical PrecisionTotal Analysis of Soils, Sediments, and Core by Various Methods (SGS Mineral Services)


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Figure 6-8. Precision plot for seven analyses of USGS standard reference material SAR–L by single-element methods. %RSD is percent relative standard deviation; RL is reporting limit.

Analysis of Analytical AccuracyTotal Analysis of Soils, Sediments and Core by Various Methods (SGS Mineral Services)


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Figure 6-9. Accuracy plot for seven analyses of USGS standard reference material SAR–L by single-element methods. RL is reporting limit.


Table 6-7. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–M; determined after a four-acid total digestion of soil samples by the ICPAES–MS42 multielement package at SGS Minerals.




Ag ppm 1 8 3.1 3.63 0.518 14.3 117Al % 0.01 8 6.09 5.84 0.231 3.96 95.8As ppm 1 8 37 38.8 2.31 5.97 105Ba ppm 5 8 764 744 56.9 7.65 97.4Be ppm 0.1 8 2.4 2.64 0.737 27.9 110Bi ppm 0.04 8 1.33 1.75 0.137 7.82 131Ca % 0.01 8 0.58 0.549 0.038 6.85 94.6Cd ppm 0.1 8 4.76 5.26 0.288 5.46 111Ce ppm 0.05 8 120 109 8.44 7.76 90.6Co ppm 0.1 8 11 11.3 0.623 5.5 103Cr ppm 1 8 101 85 4.78 5.62 84.2Cs ppm 5 8 4.8 5.25 0.463 8.82 109Cu ppm 0.5 8 320 290 12.4 4.27 90.6Fe % 0.01 8 3.22 3.08 0.15 4.88 95.7Ga ppm 0.05 8 20 16.7 1.85 11.1 83.7In ppm 0.02 8 0.97 1.06 0.061 5.8 109K % 0.01 8 2.92 2.7 0.192 7.1 92.4La ppm 0.5 8 61 51.9 4.45 8.59 85Li ppm 1 8 30 26.8 0.707 2.64 89.2

Mg % 0.01 8 0.5 0.456 0.021 4.53 91.3Mn ppm 5 8 5,200 4,910 194 3.96 94.3Mo ppm 0.05 8 12 13.5 0.967 7.17 112Na % 0.01 8 1.19 1.14 0.070 6.13 95.5Nb ppm 0.1 8 31 29.5 4.86 16.5 95.1Ni ppm 0.5 8 41 38.2 1.37 3.58 93.2P ppm 50 8 800 639 28 4.38 79.8

Pb ppm 0.5 8 960 879 32.2 3.67 91.5Rb ppm 0.2 8 142 149 6.78 4.56 105S % 0.01 8 0.13 0.123 0.013 10.5 94.2Sb ppm 0.05 8 5.6 6.85 0.328 4.79 122Sc ppm 0.1 8 8.3 7.64 0.54 7.07 92Sn ppm 0.1 8 9.4 2.94 0.381 13 31.3Sr ppm 0.5 8 156 143 4.1 2.87 91.5Te ppm 0.1 8 0.68 0.963 0.052 5.38 142Th ppm 0.2 8 18 16.1 1.53 9.53 89.2Ti % 0.01 8 0.35 0.241 0.010 4.11 68.9Tl ppm 0.1 8 2.8 2.64 0.119 4.5 94.2U ppm 0.1 8 5.1 3.36 0.233 6.92 65.9V ppm 1 8 66 64.6 3.11 4.82 97.9W ppm 0.1 8 14 9.4 1.08 11.5 67.1Y ppm 0.1 8 33 25.1 1.66 6.62 76Zn ppm 1 8 888 868 49.3 5.68 97.8



based on Standard Reference Material SAR-M

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Figure 6-10. Precision plot for eight analyses of USGS standard reference material SAR–M by ICPAES–MS42. %RSD is percent relative standard deviation; RL is reporting limit.



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Figure 6-11. Accuracy plot for eight analyses of USGS standard reference material SAR–M by ICPAES–MS42. RL is reporting limit.


Table 6-8. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–M; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals.—Continued




Ag ppm 1.0 8 3.1 3.25 0.886 27.3 105Al % 0.01 8 6.09 6.29 0.259 4.12 103As ppm 30 8 37 33.8 5.18 15.3 91.2Ba ppm 0.5 8 764 788 60.5 7.68 103Be ppm 5.0 8 5 5.76 2.32 40.4 128Bi ppm 0.1 8 1.33 1.5 0.107 7.13 113Ca % 0.01 8 0.58 0.603 0.136 22.5 104Cd ppm 0.2 8 4.76 4.71 0.36 7.65 99Ce ppm 0.1 8 120 110 9.42 8.59 91.4Co ppm 0.5 8 11 10.8 0.595 5.51 98.2Cr ppm 10 8 101 111 16.4 14.8 110Cs ppm 0.1 8 4.8 4.76 0.362 7.61 99.2Cu ppm 5.0 8 320 293 24.5 8.36 91.6Dy ppm 0.05 8 NA 7.18 0.388 5.4 NAEr ppm 0.05 8 NA 4.36 0.356 8.17 NAEu ppm 0.05 8 0.67 1.24 0.064 5.21 184Fe % 0.01 8 3.22 3.16 0.094 2.96 98.1Ga ppm 1.0 8 20 17.8 1.91 10.8 88.8Gd ppm 0.05 8 NA 7.79 0.494 6.34 NAGe ppm 1.0 8 NA 1.25 0.463 37 NAHf ppm 1.0 8 NA 9.38 0.916 9.77 NAHo ppm 0.05 8 1.9 1.43 0.162 11.3 75.5In ppm 0.2 8 0.97 0.963 0.092 9.52 99.2K % 0.01 8 2.92 2.81 0.127 4.51 96.4La ppm 0.1 8 61 53.9 4.08 7.57 88.3Li ppm 10 8 30 32.5 12.8 39.4 108Lu ppm 0.05 8 0.7 0.655 0.062 9.48 93.6Mg % 0.01 8 0.5 0.471 0.028 5.94 94.3Mn % 0.001 8 0.52 0.483 0.021 4.25 92.8Mo ppm 2.0 8 12 12 0.756 6.3 100Nb ppm 1 8 31 36.3 2.12 5.85 117Nd ppm 0.1 8 53.4 45.3 3.01 6.65 84.7Ni ppm 5.0 8 41 71.1 35 49.2 173P % 0.01 8 0.08 0.07 0.008 10.8 87.5

Pb ppm 5.0 8 960 919 68.8 7.49 95.7Pr ppm 0.05 8 NA 12.1 0.466 3.85 NARb ppm 0.2 8 142 153 3.31 2.17 108Sb ppm 0.1 8 5.6 6.38 0.167 2.62 114Sc ppm 5.0 8 8.3 8.75 2.87 32.8 105Sm ppm 0.1 8 9.8 8.39 0.584 6.96 85.6Sn ppm 1.0 8 9.4 4.88 2.95 60.5 51.9


Table 6-8. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–M; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals.—Continued




Sr ppm 0.1 8 156 150 6.58 4.39 96.1Ta ppm 0.5 8 2.6 1.94 0.092 4.73 74.5Tb ppm 0.05 8 1.3 1.21 0.086 7.17 92.7Th ppm 0.1 8 18 18.7 2.71 14.5 104Ti % 0.01 8 0.35 0.358 0.017 4.67 102Tl ppm 0.5 8 2.8 2.46 0.119 4.82 87.9

Tm ppm 0.05 8 NA 0.634 0.081 12.8 NAU ppm 0.05 8 5.1 4.34 0.298 6.85 85.1V ppm 5.0 8 66 71.9 5.91 8.23 109W ppm 1.0 8 14 8.63 1.06 12.3 61.6Y ppm 0.5 8 33 39 3.66 9.4 118

Yb ppm 0.1 8 4.9 4.26 0.563 13.2 87Zn ppm 5.0 8 888 893 102 11.5 101Zr ppm 0.5 8 370 341 22.9 6.72 92.2



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Figure 6-12. Precision plot for eight analyses of USGS standard reference material SAR–M by ICPAES–MS55. %RSD is percent relative standard deviation; RL is reporting limit.




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Figure 6-13. Accuracy plot for eight analyses of USGS standard reference material SAR–M by ICPAES–MS55. RL is reporting limit.

Table 6-9. Summary statistics for assessing analytical variation on the USGS standard reference material SAR–M; determined by various methods at SGS Minerals.




Sb_Hyd ppm 0.6 8 5.6 5.94 0.51 8.58 106Se_Hyd ppm 0.2 8 0.33 0.363 0.052 14.3 110

Hg_CVAA ppm 0.02 4 0.117 0.113 0.010 8.51 96.2Au_FA ppm 0.005 6 0.345 0.318 0.092 28.8 92.1Cl_ISE ppm 50 8 115 123 10.4 8.45 107F_ISE ppm 20 8 930 830 29.3 3.53 89.2CO2 % 0.01 8 0.07 0.083 0.013 15.5 118

Carb CO2 % 0.003 8 0.02 0.021 0.004 16.6 106Org C % 0.05 8 0.28 0.33 0.019 5.61 118Tot C % 0.01 8 0.3 0.351 0.019 5.37 117




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Figure 6-14. Precision plot for eight analyses of USGS standard reference material SAR–M by single-element methods. %RSD is percent relative standard deviation; RL is reporting limit.

Analysis of Analytical AccuracyTotal Analysis of Soils, Sediment, and Core by Various Methods (SGS Mineral Services)


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Figure 6-15. Accuracy plot for eight analyses of USGS standard reference material SAR–M by single-element methods. RL is reporting limit.


Table 6-10. Summary statistics for assessing analytical variation on the USGS standard reference material DGPM; determined after a four-acid total digestion of soil samples by the ICPAES–MS42 multielement package at SGS Minerals.




Ag ppm 1.0 3 1 <1 NA NA 100Al % 0.01 3 4.94 4.8 0.227 4.73 97.2As ppm 1.0 3 177 186 7.81 4.2 105Ba ppm 5.0 3 1,326 1,230 120 9.79 92.5Be ppm 0.1 3 1.543 2 0.436 21.8 130Bi ppm 0.04 3 0.114 0.117 0.012 9.9 102Ca % 0.01 3 0.144 0.13 0.01 7.69 90.3Cd ppm 0.1 3 0.33 0.333 0.058 17.3 101Ce ppm 0.05 3 91.3 91.8 2.17 2.36 101Co ppm 0.1 3 1.364 1.53 0.153 9.96 112Cr ppm 1.0 3 97 98.7 23.1 23.4 102Cs ppm 5.0 3 8.865 9.33 0.577 6.19 105Cu ppm 0.5 3 13.67 14.2 4.18 29.4 104Fe % 0.01 3 1.343 1.36 0.095 6.97 102Ga ppm 0.05 3 10.8 11.2 0.351 3.14 103In ppm 0.02 3 0.02 <0.02 NA NA 103K % 0.01 3 2.247 2.14 0.085 3.99 95.2La ppm 0.5 3 51.46 49.2 4.85 9.86 95.6Li ppm 1.0 3 39.6 38 1 2.63 96

Mg % 0.01 3 0.322 0.303 0.012 3.81 94.2Mn ppm 5.0 3 28.01 28.3 1.53 5.39 101Mo ppm 0.05 3 13.69 14.5 0.896 6.2 106Na % 0.01 3 0.06 0.057 0.006 10.2 94.4Nb ppm 0.1 3 7.2 7.6 0.458 6.03 106Ni ppm 0.5 3 11.36 9.73 0.603 6.19 85.7P ppm 50 3 418 380 10 2.63 90.9

Pb ppm 0.5 3 9.78 12.1 3.82 31.5 124Rb ppm 0.2 3 89.8 94.4 4.15 4.39 105S % 0.01 3 0.363 0.337 0.051 15.2 92.7Sb ppm 0.05 3 13.2 14.2 0.265 1.86 108Sc ppm 0.1 3 9.83 9.9 0.557 5.62 101Sn ppm 0.1 3 1.81 1.77 0.058 3.27 97.6Sr ppm 0.5 3 91.5 87.2 3.06 3.51 95.3Te ppm 0.1 3 0.1 <0.1 NA NA 100Th ppm 0.2 3 10.7 10.9 0.513 4.69 102Ti % 0.01 3 0.266 0.243 0.025 10.3 91.5Tl ppm 0.1 3 8.15 8.77 0.643 7.33 108U ppm 0.1 3 2.75 2.73 0.058 2.11 99.4V ppm 1.0 3 106 106 7.23 6.85 99.7W ppm 0.1 3 75 78.1 1.92 2.45 104Y ppm 0.1 3 17.5 17.3 0.929 5.36 99Zn ppm 1.0 3 24.4 21 1 4.76 86.1


Analysis of Analytical PrecisionICPAES-MS42 Total Analysis of Soils and Sediments (SGS Mineral Services)

based on Standard Reference Material DGPM

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pmTh

_ppm

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_ppm

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_ppm

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pmZn

_ppm

Elements

% R

SD


Figure 6-16. Precision plot for three analyses of USGS standard reference material DGPM by ICPAES–MS42. %RSD is percent relative standard deviation; RL is reporting limit.

Analysis of Analytical AccuracyICPAES-MS42 Total Analysis of Soils and Sediments (SGS Mineral Services)


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_ppm

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pmZn

_ppm

Elements

% R

ecov

ery


Figure 6-17. Accuracy plot for three analyses of USGS standard reference material DGPM by ICPAES–MS42. RL is reporting limit.


Table 6-11. Summary statistics for assessing analytical variation on the USGS standard reference material DGPM; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals.—Continued




Ag ppm 1.0 3 1 <1 NA NA 100Al % 0.01 3 4.82 5.11 0.122 2.39 106As ppm 30 3 169 175 18 10.3 104Ba ppm 0.5 3 1,272 1,280 103 8.04 100Be ppm 5.0 3 5 5.34 1.44 26.9 118Bi ppm 0.1 3 0.1 <0.1 NA NA 107Ca % 0.01 3 0.17 0.2 0.046 22.9 118Cd ppm 0.2 3 0.34 0.3 0 0 88.2Ce ppm 0.1 3 90.5 63.8 52.4 82.2 70.5Co ppm 0.5 3 1.36 1.5 0.173 11.5 110Cr ppm 10 3 120 133 25.2 18.9 111Cs ppm 0.1 3 8.92 9 0.5 5.56 101Cu ppm 5.0 3 13 13.3 4.16 31.2 103Dy ppm 0.05 3 3.22 3.54 0.225 6.36 110Er ppm 0.05 3 2.08 2.14 0.087 4.08 103Eu ppm 0.05 3 0.78 0.733 0.032 4.38 94Fe % 0.01 3 1.36 1.39 0.017 1.25 102Ga ppm 1.0 3 11.3 11 1 9.09 97.3Gd ppm 0.05 3 3.9 3.95 0.025 0.637 101Ge ppm 1.0 3 2.34 2 0 0 85.5Hf ppm 1.0 3 9.82 10.7 0.577 5.41 109Ho ppm 0.05 3 0.668 0.687 0.015 2.22 103In ppm 0.2 3 0.2 <0.2 NA NA 100K % 0.01 3 2.23 2.25 0.075 3.34 101La ppm 0.1 3 51.7 53.9 2.97 5.52 104Li ppm 10 3 41.9 46.7 11.5 24.7 111Lu ppm 0.05 3 0.315 0.36 0.036 10 114Mg % 0.01 3 0.322 0.31 0.01 3.23 96.3Mn % 0.001 3 0.003 0.004 0.005 133 158Mo ppm 2.0 3 13.6 12.7 0.577 4.56 93.1Nb ppm 1.0 3 9.8 9.67 0.577 5.97 98.6Nd ppm 0.1 3 30.5 30.2 0.361 1.19 99Ni ppm 5.0 3 14.3 30.5 37.1 122 213P % 0.01 3 0.041 0.043 0.006 13.3 106

Pb ppm 5.0 3 10 10 0 0 100Pr ppm 0.05 3 9.43 9.49 0.326 3.43 101Rb ppm 0.2 3 94 97.9 5.45 5.57 104Sb ppm 0.1 3 13 12.7 0.1 0.787 97.7Sc ppm 5.0 3 8.79 10 2 20 114Sm ppm 0.1 3 4.7 4.83 0.058 1.19 103Sn ppm 1.0 3 1.8 2.33 0.577 24.7 130


Table 6-11. Summary statistics for assessing analytical variation on the USGS standard reference material DGPM; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals.—Continued




Sr ppm 0.1 3 91 88.4 7.85 8.89 97.1Ta ppm 0.5 3 0.67 0.617 0.175 28.4 92.1Tb ppm 0.05 3 0.599 0.593 0.031 5.15 99.1Th ppm 0.1 3 9.9 10.7 0.3 2.8 108Ti % 0.01 3 0.325 0.32 0.01 3.13 98.5Tl ppm 0.5 3 8.21 8.43 0.306 3.62 103

Tm ppm 0.05 3 0.295 0.303 0.025 8.3 103U ppm 0.05 3 3.26 3.48 0.244 7.02 107V ppm 5.0 3 104 107 8.54 7.99 103W ppm 1.0 3 73.6 76.3 1.15 1.51 104Y ppm 0.5 3 19.9 20.2 0.7 3.47 102

Yb ppm 0.1 3 2.05 2.1 0.173 8.25 102Zn ppm 5.0 3 22 29.3 16.3 55.5 133Zr ppm 0.5 3 410 378 12.5 3.31 92.1

Analysis of Analytical PrecisionICPAES-MS55 Total Analysis of Soils and Sediments (SGS Mineral Services)


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_ppm

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_ppm

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pmY

b_pp

mZn

_ppm

Zr_p

pm

Elements

% R

SD


Figure 6-18. Precision plot for three analyses of USGS standard reference material DGPM by ICPAES–MS55. %RSD is percent relative standard deviation; RL is reporting limit.


Analysis of Analytical AccuracyICPAES-MS55 Total Analysis of Soils and Sediments (SGS Mineral Services)


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_ppm

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pmY

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mZn

_ppm

Zr_p

pm

Elements

% R

ecov

ery


Figure 6-19. Accuracy plot for three analyses of USGS standard reference material DGPM by ICPAES–MS55. RL is reporting limit.

Table 6-12. Summary statistics for assessing analytical variation on the USGS standard reference material DGPM; determined by various methods at SGS Minerals.




Sb_Hyd ppm 0.6 3 14 15.8 1.35 8.51 113Se_Hyd ppm 0.2 3 1.24 1.3 0 0 105

Hg_CVAA ppm 0.02 1 1.08 1.08 NA NA 100Au_FA ppm 0.005 1 0.73 0.654 NA NA 89.6Cl_ISE ppm 50 3 347 323 5.77 1.79 93.2F_ISE ppm 20 3 944 863 28.9 3.34 91.5CO2 % 0.01 3 0.03 0.027 0.006 21.7 88.9

Carb CO2 % 0.003 3 0.01 0.01 0 0 100Org C % 0.05 2 0.09 0.12 0 0 133Tot C % 0.01 3 0.1 0.123 0.012 9.36 123


Analysis of Analytical PrecisionTotal Analysis of Soils and Sediments by Various Methods (SGS Mineral Services)


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_ppm

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pm

CO

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_C_%

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Figure 6-20. Precision plot for three analyses of USGS standard reference material DGPM by single-element methods. %RSD is percent relative standard deviation; RL is reporting limit.

Analysis of Analytical AccuracyTotal Analysis of Soils and Sediments by Various Methods (SGS Mineral Services)


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ecov

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Figure 6-21. Accuracy plot for three analyses of USGS standard reference material DGPM by single-element methods. RL is reporting limit.


Table 6-13. Summary statistics for assessing analytical variation on the USGS standard reference material GSP–QC; determined after a four-acid total digestion of soil samples by the ICPAES–MS42 multielement package at SGS Minerals.




Ag ppm 1.0 4 3.07 3.5 0.577 16.5 114Al % 0.01 4 7.57 7.07 0.328 4.65 93.3As ppm 1.0 4 31.4 36.8 2.5 6.8 117Ba ppm 5.0 4 1,310 1,240 69 5.55 94.8Be ppm 0.1 4 1.174 1.48 0.126 8.53 126Bi ppm 0.04 4 4.28 4.49 0.263 5.87 105Ca % 0.01 4 1.5 1.38 0.133 9.67 91.8Cd ppm 0.1 4 0.227 0.225 0.05 22.2 99.1Ce ppm 0.05 4 405 417 29.6 7.09 103Co ppm 0.1 4 6.36 7.15 0.58 8.12 112Cr ppm 1.0 4 16.6 20 2.71 13.5 120Cs ppm 5.0 4 1.99 <5 NA NA 227Cu ppm 0.5 4 31.3 29 2.12 7.33 92.7Fe % 0.01 4 2.77 2.72 0.121 4.45 98Ga ppm 0.05 4 22.2 23.5 0.206 0.876 106In ppm 0.02 4 0.044 0.048 0.005 10.5 108K % 0.01 4 4.25 3.69 0.319 8.64 86.8La ppm 0.5 4 173 180 13.6 7.58 104Li ppm 1.0 4 34 31 2.16 6.97 91.2

Mg % 0.01 4 0.615 0.548 0.022 4.05 89Mn ppm 5.0 4 281 260 8.69 3.35 92.4Mo ppm 0.05 4 1.31 1.45 0.173 12 110Na % 0.01 4 1.87 1.73 0.046 2.63 92.5Nb ppm 0.1 4 18.6 19.2 0.842 4.39 103Ni ppm 0.5 4 11.5 8.43 0.544 6.46 73.3P ppm 50 4 1,230 1,120 32 2.86 90.9

Pb ppm 0.5 4 40.4 43.9 3.4 7.74 109Rb ppm 0.2 4 228 245 16.3 6.67 107S % 0.01 4 0.074 0.063 0.005 8 84.5Sb ppm 0.05 4 0.877 0.933 0.031 3.32 106Sc ppm 0.1 4 6.23 6.63 0.359 5.42 106Sn ppm 0.1 4 4.72 4.93 0.126 2.55 104Sr ppm 0.5 4 226 203 14.8 7.27 89.8Te ppm 0.1 4 4.07 4.33 0.263 6.08 106Th ppm 0.2 4 104 113 9.06 8.01 109Ti % 0.01 4 0.339 0.298 0.019 6.36 87.8Tl ppm 0.1 4 2.07 2.2 0.141 6.43 106U ppm 0.1 4 2.27 2.3 0 0 101V ppm 1.0 4 73.3 71 4.83 6.8 96.9W ppm 0.1 4 6.65 6.85 0.265 3.86 103Y ppm 0.1 4 25.5 24.6 1.49 6.07 96.5Zn ppm 1.0 4 117 109 1.73 1.6 92.7



based on Standard Reference Material GSP-QC

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Elements

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Figure 6-22. Precision plot for four analyses of USGS standard reference material GSP–QC by ICPAES–MS42. %RSD is percent relative standard deviation; RL is reporting limit.



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% R

ecov

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Figure 6-23. Accuracy plot for four analyses of USGS standard reference material GSP–QC by ICPAES–MS42. RL is reporting limit.


Table 6-14. Summary statistics for assessing analytical variation on the USGS standard reference material GSP–QC; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals.—Continued




Ag ppm 1.0 4 2.75 3.5 0.577 16.5 127Al % 0.01 4 7.4 7.87 0.302 3.84 106As ppm 30 4 30 <30 NA NA 108Ba ppm 0.5 4 1,320 1,360 98 7.2 103Be ppm 5.0 4 5 <5 NA NA 100Bi ppm 0.1 4 4.3 4.43 0.05 1.13 103Ca % 0.01 4 1.55 1.44 0.070 4.84 92.9Cd ppm 0.2 4 0.262 0.3 0.082 27.2 115Ce ppm 0.1 4 369 423 23.4 5.54 115Co ppm 0.5 4 6.37 6.65 0.191 2.88 104Cr ppm 10 4 22.1 30 14.1 47.1 136Cs ppm 0.1 4 1.99 2.03 0.096 4.73 102Cu ppm 5.0 4 31.1 30.8 3.77 12.3 98.9Dy ppm 0.05 4 5.56 5.93 0.326 5.5 107Er ppm 0.05 4 2.64 2.49 0.101 4.06 94.1Eu ppm 0.05 4 2.02 2.12 0.061 2.9 105Fe % 0.01 4 2.85 2.88 0.047 1.64 101Ga ppm 1.0 4 22 23 2.45 10.6 105Gd ppm 0.05 4 14.8 15.4 0.709 4.6 104Ge ppm 1.0 4 1.62 1.5 0.577 38.5 92.6Hf ppm 1.0 4 9.69 14.8 0.957 6.49 152Ho ppm 0.05 4 0.924 0.97 0.014 1.46 105In ppm 0.2 4 0.2 <0.2 NA NA 100K % 0.01 4 4.12 4.02 0.103 2.56 97.6La ppm 0.1 4 166 181 2.31 1.28 109Li ppm 10 4 33.6 32.5 5 15.4 96.7Lu ppm 0.05 4 0.248 0.265 0.027 9.98 107Mg % 0.01 4 0.599 0.578 0.025 4.33 96.4Mn % 0.001 4 0.027 0.03 0 0 111Mo ppm 2.0 4 2 2.61 1.59 61.1 144Nb ppm 1.0 4 22.6 24.3 1.71 7.04 107Nd ppm 0.1 4 186 194 3.2 1.65 104Ni ppm 5.0 4 10.6 27.4 29.7 109 258P % 0.01 4 0.118 0.123 0.010 7.82 104

Pb ppm 5.0 4 43.3 43.5 1.73 3.98 100Pr ppm 0.05 4 47.7 52.2 1.51 2.89 109Rb ppm 0.2 4 240 249 9.13 3.67 104Sb ppm 0.1 4 0 0.8 0 0 NASc ppm 5.0 4 5.75 5.88 1.54 26.3 102Sm ppm 0.1 4 23.8 24.8 0.351 1.42 104


Table 6-14. Summary statistics for assessing analytical variation on the USGS standard reference material GSP–QC; determined after a sodium peroxide sinter of soil samples by the ICPAES–MS55 multielement package at SGS Minerals.—Continued




Sn ppm 1 4 4.88 5.25 0.5 9.52 108Sr ppm 0.1 4 219 215 10.8 5.04 98.1Ta ppm 0.5 4 7.99 8.03 0.206 2.57 100Tb ppm 0.05 4 1.68 1.66 0.054 3.27 99Th ppm 0.1 4 99.9 106 4.99 4.7 106Ti % 0.01 4 0.376 0.378 0.010 2.54 100Tl ppm 0.5 4 2.11 2.2 0.082 3.71 104

Tm ppm 0.05 4 0.271 0.295 0.017 5.87 109U ppm 0.05 4 2.56 2.55 0.047 1.84 99.6V ppm 5.0 4 72.8 75.8 7.14 9.42 104W ppm 1.0 4 6.33 6.5 0.577 8.88 103Y ppm 0.5 4 25 25.4 0.64 2.53 101

Yb ppm 0.1 4 1.71 1.83 0.05 2.74 107Zn ppm 5.0 4 115 119 7.16 6.02 103Zr ppm 0.5 4 396 522 18.4 3.52 132

Analysis of Analytical PrecisionICPAES-MS55 Total Analysis of Soils, Sediments and Core (SGS Mineral Services)


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pm

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% R

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Figure 6-24. Precision plot for four analyses of USGS standard reference material GSP–QC by ICPAES–MS55. %RSD is percent relative standard deviation; RL is reporting limit.


Analysis of Analytical AccuracyICPAES-MS55 Total Analysis of Soils, Sediment, and Core (SGS Mineral Services)


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Figure 6-25. Accuracy plot for four analyses of USGS standard reference material GSP–QC by ICPAES–MS55. RL is reporting limit.

Table 6-15. Summary statistics for assessing analytical variation on the USGS standard reference material GSP–QC; determined by various methods at SGS Minerals.




Sb_Hyd ppm 0.6 4 NA 0.8 0.082 10.2 NASe_Hyd ppm 0.2 4 3.97 3.95 0.238 6.03 99.5

Hg_CVAA ppm 0.02 2 0.26 0.245 0.007 2.89 94.2Au_FA ppm 0.005 3 0.156 0.152 0.012 7.59 97.4Cl_ISE ppm 50 4 372 343 20.6 6.02 92.1F_ISE ppm 20 4 3,100 3,160 32 1.01 102CO2 % 0.01 4 0.33 0.33 0.008 2.47 100

Carb CO2 % 0.003 4 0.09 0.09 0 0 100Org C % 0.05 4 NA 0.133 0.017 12.9 NATot C % 0.01 4 0.18 0.223 0.017 7.68 124




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Figure 6-26. Precision plot for four analyses of USGS standard reference material GSP–QC by single-element methods. %RSD is percent relative standard deviation; RL is reporting limit.

Analysis of Analytical AccuracyTotal Analysis of Soils, Sediments, and Core by Various Methods (SGS Mineral Services)


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Figure 6-27. Accuracy plot for four analyses of USGS standard reference material GSP–QC by single-element methods. RL is reporting limit.


Table 6-16. Summary statistics for assessing analytical variation on the Pebble project standard reference material PB–SMM; determined after a four-acid total digestion of soil, pond and stream sediment, and pond core sediment samples by the ICPAES–MS42 multielement package at SGS Minerals.




Ag ppm 1.0 20 1 <1 NA NA NAAl % 0.01 20 7.694 8.13 0.372 4.57 106As ppm 1.0 20 15.8 15.4 0.821 5.33 97.5Ba ppm 5.0 20 761 736 51.6 7.01 96.7Be ppm 0.1 20 1.42 1.31 0.427 32.6 92.3Bi ppm 0.04 20 0.214 0.25 0.041 16.4 117Ca % 0.01 20 1.52 1.46 0.105 7.2 96.3Cd ppm 0.1 20 0.24 <0.1 NA NA 41.5Ce ppm 0.05 20 39.02 38.8 2.72 7.01 99.3Co ppm 0.1 20 13.98 14.2 0.587 4.13 102Cr ppm 1.0 20 50.8 51.9 4.13 7.95 102Cs ppm 5.0 20 5 <5 NA NA 90.2Cu ppm 0.5 20 133.6 139 8.6 6.19 104Fe % 0.01 20 4.432 4.61 0.188 4.06 104Ga ppm 0.05 20 18.14 15.9 2.31 14.6 87.4In ppm 0.02 20 0.066 0.061 0.004 6.51 91.7K % 0.01 20 1.326 1.38 0.116 8.41 104La ppm 0.5 20 18.16 19.3 1.47 7.62 106Li ppm 1.0 20 19.2 19.4 1.5 7.73 101

Mg % 0.01 20 0.882 0.833 0.056 6.76 94.4Mn ppm 5.0 20 761.2 760 43.6 5.74 99.8Mo ppm 0.05 20 4.186 4.14 0.415 10 99Na % 0.01 20 1.642 1.73 0.1 5.8 106Nb ppm 0.1 20 10 10.2 1.36 13.4 102Ni ppm 0.5 20 16.34 16.1 1.65 10.3 98.4P ppm 50 20 1204 1140 51.3 4.5 94.5

Pb ppm 0.5 20 17.78 15.1 1.16 7.68 84.8Rb ppm 0.2 20 45.84 47.6 2.42 5.09 104S % 0.01 20 0.082 0.056 0.005 8.98 68.3Sb ppm 0.05 20 1.266 1.29 0.076 5.88 102Sc ppm 0.1 20 16.22 14.4 1.25 8.67 89.1Sn ppm 0.1 20 1.38 1.43 0.133 9.35 103Sr ppm 0.5 20 237.4 247 14.5 5.87 104Te ppm 0.1 20 0.2 0.16 0.050 31.4 80Th ppm 0.2 20 4.22 4.2 0.162 3.86 99.5Ti % 0.01 20 0.532 0.505 0.031 6.15 94.9Tl ppm 0.1 20 0.4 0.42 0.041 9.77 105U ppm 0.1 20 1.94 2.05 0.119 5.82 106V ppm 1.0 20 132.8 131 7.67 5.87 98.3W ppm 0.1 20 1.18 1.01 0.173 17.2 85.2Y ppm 0.1 20 17.3 18.3 0.974 5.32 106Zn ppm 1.0 20 89 70.9 3.34 4.71 79.7


Analysis of Analytical PrecisionICPAES-MS42 Total Analysis of Soil, Sediment, and Core (SGS Mineral Services)


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Elements

% R

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Figure 6-28. Precision plot for 20 analyses of Pebble project standard reference material PB–SMM by ICPAES–MS42. %RSD is percent relative standard deviation; RL is reporting limit.

Analysis of Analytical AccuracyICPAES-MS42 Total Analysis of Soil, Sediment, and Core (SGS Mineral Services)


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pmZn

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Elements

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ecov

ery


Figure 6-29. Accuracy plot for 20 analyses of Pebble project standard reference material PB–SMM by ICPAES–MS42. RL is reporting limit.


Table 6-17. Summary statistics for assessing analytical variation on the Pebble project standard reference material PB–SMM; determined after a sodium peroxide sinter of soil, pond and stream sediment, and pond core sediment samples by the ICPAES–MS55 multielement package at SGS Minerals.—Continued




Ag ppm 1.0 20 1.53 <1 NA NA 64.6Al % 0.01 20 7.714 8.35 0.399 4.79 108As ppm 30 20 30 <30 NA NA 90.4Ba ppm 0.5 20 720.8 774 52.3 6.75 107Be ppm 5.0 20 5.01 <5 NA NA 90.1Bi ppm 0.1 20 0.2 0.225 0.055 24.4 113Ca % 0.01 20 1.526 1.53 0.080 5.26 100Cd ppm 0.2 20 0.2 0.204 0.067 32.9 102Ce ppm 0.1 20 39.1 42.8 2.31 5.38 110Co ppm 0.5 20 12.92 14.2 1.03 7.27 110Cr ppm 10 20 56 66 8.21 12.4 118Cs ppm 0.1 20 3.12 3.2 0.22 6.88 103Cu ppm 5.0 20 123.6 133 9.48 7.12 108Dy ppm 0.05 20 4.182 4.12 0.16 3.88 98.4Er ppm 0.05 20 2.47 2.46 0.14 5.71 99.5Eu ppm 0.05 20 1.176 1.19 0.040 3.41 101Fe % 0.01 20 4.55 4.65 0.127 2.72 102Ga ppm 1.0 20 17.8 18 1.84 10.2 101Gd ppm 0.05 20 4.282 4.61 0.216 4.7 108Ge ppm 1.0 20 2 1.65 0.489 29.7 82.5Hf ppm 1.0 20 5 5.15 0.587 11.4 103Ho ppm 0.05 20 0.854 0.817 0.032 3.89 95.7In ppm 0.2 20 0.2 <0.2 NA NA 90.6K % 0.01 20 1.372 1.38 0.082 5.96 100La ppm 0.1 20 18.14 20.9 1.26 6.03 115Li ppm 10 20 16 18 4.1 22.8 113Lu ppm 0.05 20 0.376 0.367 0.028 7.63 97.5Mg % 0.01 20 0.808 0.828 0.029 3.46 102Mn % 0.001 20 0.07 0.075 0.005 6.85 106Mo ppm 2.0 20 4.6 3.95 0.51 12.9 85.9Nb ppm 1.0 20 11.8 10.9 0.745 6.87 91.9Nd ppm 0.1 20 19.38 20.7 0.886 4.28 107Ni ppm 5.0 20 14.8 26.5 6.88 26 179P % 0.01 20 0.118 0.119 0.006 4.95 100

Pb ppm 5.0 20 15.6 16.4 2.35 14.3 105Pr ppm 0.05 20 4.802 5.07 0.307 6.06 106Rb ppm 0.2 20 45.86 49.1 1.68 3.41 107Sb ppm 0.1 20 1.34 1.43 0.802 56.3 106Sc ppm 5.0 20 14.2 12.8 2.61 20.4 90.1Sm ppm 0.1 20 4.54 4.47 0.195 4.36 98.5


Table 6-17. Summary statistics for assessing analytical variation on the Pebble project standard reference material PB–SMM; determined after a sodium peroxide sinter of soil, pond and stream sediment, and pond core sediment samples by the ICPAES–MS55 multielement package at SGS Minerals.—Continued




Sn ppm 1.0 20 3.6 2.85 3 105 79Sr ppm 0.1 20 274.6 244 10.9 4.49 88.7Ta ppm 0.5 20 0.66 0.65 0.069 10.6 98.5Tb ppm 0.05 20 0.734 0.693 0.033 4.78 94.3Th ppm 0.1 20 4.18 4.64 0.244 5.25 111Ti % 0.01 20 0.552 0.567 0.027 4.8 103Tl ppm 0.5 20 0.5 <0.5 NA NA 90.2

Tm ppm 0.05 20 0.36 0.358 0.014 3.8 99.4U ppm 0.05 20 2.282 2.27 0.087 3.84 99.6V ppm 5.0 20 122 135 3.88 2.87 111W ppm 1.0 20 2 2.05 0.224 10.9 103Y ppm 0.5 20 22.64 21.8 0.585 2.68 96.5

Yb ppm 0.1 20 2.5 2.42 0.095 3.93 96.8Zn ppm 5.0 20 86.4 75.1 5.24 6.98 86.9Zr ppm 0.5 20 199.8 192 20.6 10.7 96

Analysis of Analytical PrecisionICPAES-MS55 Total Analysis of Soil, Sediment, and Core (SGS Mineral Services)


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pmU

_ppm

V_p

pmW

_ppm

Y_p

pmY

b_pp

mZn

_ppm

Zr_p

pm

Elements

% R

SD


Figure 6-30. Precision plot for 20 analyses of Pebble project standard reference material PB–SMM by ICPAES–MS55. %RSD is percent relative standard deviation; RL is reporting limit.


Analysis of Analytical AccuracyICPAES-MS55 Total Analysis of Soil, Sediment, and Core (SGS Mineral Services)


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Sm

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_ppm

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_ppm

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_ppm

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_ppm

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pm

Elements

% R

ecov

ery


Figure 6-31. Accuracy plot for 20 analyses of Pebble project standard reference material PB–SMM by ICPAES–MS55. RL is reporting limit.

Table 6-18. Summary statistics for assessing analytical variation on the Pebble project standard reference material PB–SMM; determined by various methods on soil, pond and stream sediment, and pond core sediment samples at SGS Minerals.





Hg_CVAA ppm 0.02 14 0.068 0.083 0.023 28.2 122Au_FA ppm 0.005 19 0.033 0.039 0.032 83.8 116Cl_ISE ppm 50 20 130 181 34.4 19.1 139F_ISE ppm 20 20 360 303 21.5 7.11 84.2CO2 % 0.01 20 0.142 0.135 0.037 27.5 95.1

Carb CO2 % 0.003 20 0.04 0.037 0.010 26.5 92.5Org C % 0.05 20 3.55 3.66 0.097 2.66 103Tot C % 0.01 20 3.59 3.69 0.098 2.64 103


Analysis of Analytical PrecisionTotal Analysis of Soil, Sediment, and Core by Various Methods (SGS Mineral Services)


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Figure 6-32. Precision plot for 20 analyses of Pebble project standard reference material PB–SMM by single-element methods. %RSD is percent relative standard deviation; RL is reporting limit.

Analysis of Analytical AccuracyTotal Analysis of Soil, Sediment, and Core by Various Methods (SGS Mineral Services)


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Figure 6-33. Accuracy plot for 20 analyses of Pebble project standard reference material PB–SMM by single-element methods. RL is reporting limit.


Appendix 7: Quality Control Tables and Charts for Activation Laboratories, Ltd., High-Resolution ICP–MS Data

Table 7-1. Summary statistics for assessing analytical variation on the standard reference material NIST–1643e; determined by High-Resolution ICP–MS on water samples at Activation Laboratories, Ltd.—Continued




Ag ppb 0.002 3 1.062 1.03 0.008 0.74 97.3As ppb 0.04 3 60.45 57.7 1.28 2.21 95.5Au ppb 0.007 3 NA <0.007 0 NA NAB ppb 2.0 3 157.9 147 0.507 0.346 93Ba ppb 0.004 3 544.2 538 16 2.98 98.8Be ppb 0.001 3 13.98 13.7 0.141 1.03 98Bi ppb 0.000 3 14.09 14 0.526 3.76 99.4Ca ppb 0.005 3 32,300 30,800 224 0.726 95.4Cd ppb 0.000 3 6.568 6.54 0.045 0.691 99.6Ce ppb 0.002 3 NA 0.043 0.008 18.8 NACo ppb 0.001 3 27.06 26.6 0.334 1.25 98.4Cr ppb 0.006 3 20.4 20.1 0.069 0.341 98.6Cs ppb 0.001 3 NA 0.005 0.001 26.3 NACu ppb 0.01 3 22.76 22.6 0.51 2.25 99.5Dy ppb 0.000 3 NA 0.000 0.000 11.5 NAEr ppb 0.000 3 NA 0.009 0.000 2.92 NAEu ppb 0.000 3 NA 0.169 0.008 4.44 NAFe ppb 0.1 3 98.1 103 2.69 2.62 105Ga ppb 0.001 3 NA 0.026 0.004 16.8 NAGd ppb 0.000 3 NA 0.002 0.000 10 NAGe ppb 0.001 3 NA <0.001 NA NA NAHf ppb 0.000 3 NA 0.004 0.001 17.9 NAHg ppb 0.04 3 NA <0.04 NA NA NAHo ppb 0.000 3 NA 0.000 0.000 3.21 NAIn ppb 0.000 3 NA 0.003 0.000 14.3 NAK ppb 1.0 3 2,034 1,990 55.9 2.81 97.7La ppb 0.002 3 NA 0.124 0.008 6.54 NALi ppb 0.03 3 17.4 18.3 1.12 6.14 105Lu ppb 0.000 3 NA <0.00001 NA NA NAMg ppb 0.2 3 8,037 8,090 225 2.78 101Mn ppb 0.1 3 38.97 38.6 0.285 0.738 99Mo ppb 0.004 3 121.4 122 1.02 0.835 101Na ppb 20 3 20,740 20,900 62.2 0.298 101Nb ppb 0.000 3 NA 0.003 0.000 0.509 NANd ppb 0.000 3 NA 0.015 0.001 4.54 NANi ppb 0.05 3 62.41 58.3 1.82 3.12 93.4Pb ppb 0.003 3 19.63 19.5 0.154 0.788 99.2Pd ppb 0.001 3 NA 0.241 0.004 1.66 NA

Appendix 7: Quality Control Tables and Charts for Activation Laboratories, Ltd., High-Resolution ICP–MS Data 97

Table 7-1. Summary statistics for assessing analytical variation on the standard reference material NIST–1643e; determined by High-Resolution ICP–MS on water samples at Activation Laboratories, Ltd.—Continued




Pr ppb 0.000 3 NA 0.009 0.001 6.05 NAPt ppb 0.001 3 NA <0.001 NA NA NARb ppb 0.04 3 14.14 13.8 1.03 7.44 97.9Re ppb 0.000 3 NA 95.7 0.264 0.275 NARu ppb 0.001 3 NA <0.001 NA NA NASb ppb 0.001 3 58.3 57.4 0.349 0.609 98.4Sc ppb 0.01 3 NA <0.01 NA NA NASe ppb 3.0 3 11.97 11.9 0.674 5.66 99.5Sm ppb 0.000 3 NA 0.003 0.000 7.48 NASn ppb 0.006 3 NA 0.023 0.006 25.6 NASr ppb 0.01 3 323.1 323 5.71 1.77 100Ta ppb 0.001 3 NA 0.001 0.000 23.5 NATb ppb 0.000 3 NA 0.000 0.000 5.88 NATe ppb 0.001 3 1.09 1.1 0.022 1.98 101Th ppb 0.000 3 NA 0.001 0.000 8.13 NATi ppb 0.01 3 NA 0.167 0.002 1.25 NATl ppb 0.000 3 7.445 7.34 0.127 1.74 98.6

Tm ppb 0.000 3 NA <0.0001 NA NA NAU ppb 0.000 3 NA 0.002 0.000 12.4 NAV ppb 0.000 3 37.86 37.4 0.477 1.27 98.9W ppb 0.001 3 NA 0.051 0.015 29.9 NAY ppb 0.000 3 NA 0.036 0.003 7.26 NA

Yb ppb 0.000 3 NA 0.000 0.000 6.2 NAZn ppb 0.4 3 78.5 80.8 2.29 2.83 103Zr ppb 0.001 3 NA 0.021 0.002 7.34 NA


Analysis of Analytical PrecisionHigh-Resolution ICP-MS Analysis of Water (Act Labs)

based on Standard Reference Material NIST-1643e

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Figure 7-1. Precision plot for three analyses of standard reference material NIST–1643e by High-Resolution ICP–MS. %RSD is percent relative standard deviation; RL is reporting limit.

Analysis of Analytical AccuracyHigh-Resolution ICP-MS Analysis of Water (Act Labs)

Based on Standard Reference Material NIST-1643e

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Figure 7-2. Accuracy plot for three analyses of standard reference material NIST–1643e by High-Resolution ICP–MS. RL is reporting limit.


Table 7-2. Summary statistics for assessing analytical variation on the standard reference material T–159; determined by High-Resolution ICP–MS on water samples at Activation Laboratories, Ltd.—Continued




Ag ppb 0.002 8 9.67 9.53 0.936 9.82 98.5As ppb 0.04 8 28.4 39.8 2.02 5.07 140Au ppb 0.007 8 NA <0.007 NA NA NAB ppb 2.0 8 28.4 30.6 2 6.53 108Ba ppb 0.004 8 38.1 43.5 2.21 5.09 114Be ppb 0.001 8 10.8 13.9 1.2 8.58 129Bi ppb 0.000 8 NA 0.001 0.001 70.1 NACa ppb 0.005 8 25,500 27,000 1,090 4.04 106Cd ppb 0.000 8 24 28.5 1.79 6.25 119Ce ppb 0.002 8 NA 0.036 0.010 27.5 NACo ppb 0.001 8 13.3 13.4 0.86 6.43 101Cr ppb 0.006 8 26.8 29.9 1.79 5.96 112Cs ppb 0.001 8 NA 0.010 0.001 11.7 NACu ppb 0.01 8 33.4 34.3 2.26 6.6 103Dy ppb 0.000 8 NA 0.004 0.001 11.8 NAEr ppb 0.000 8 NA 0.003 0.000 13.5 NAEu ppb 0.000 8 NA 0.020 0.011 58.5 NAFe ppb 0.1 8 48.9 52.8 4.02 7.61 108Ga ppb 0.001 8 NA 0.021 0.003 14.3 NAGd ppb 0.000 8 NA 0.003 0.001 21.4 NAGe ppb 0.001 8 NA 0.011 0.004 33.8 NAHf ppb 0.000 8 NA 0.002 0.001 61.6 NAHg ppb 0.04 8 NA 0.191 0.316 166 NAHo ppb 0.000 8 NA 0.001 0.000 5.66 NAIn ppb 0.000 8 NA 0.025 0.002 9.29 NAK ppb 1.0 8 1,520 1,680 68.3 4.06 110La ppb 0.002 8 NA 0.044 0.022 50.6 NALi ppb 0.03 8 8.97 8.99 3.86 43 100Lu ppb 0.000 8 NA 0.000 0.000 17.2 NAMg ppb 0.2 8 5,600 5,470 1,370 25.1 97.6Mn ppb 0.1 8 22 23.6 1.51 6.39 107Mo ppb 0.004 8 41.4 46.9 2.98 6.36 113Na ppb 20 8 100,000 79,500 39,300 49.4 79.5Nb ppb 0.000 8 NA 0.003 0.002 47.3 NANd ppb 0.000 8 NA 0.023 0.003 11.5 NANi ppb 0.05 8 22.2 20.8 1.47 7.07 93.9Pb ppb 0.003 8 16.6 14.6 1.08 7.38 87.8Pd ppb 0.001 8 NA 0.757 0.080 10.5 NAPr ppb 0.000 8 NA 0.006 0.002 29.4 NAPt ppb 0.001 8 NA <0.001 --- na NARb ppb 0.04 8 NA 1.08 0.075 6.97 NA






Re ppb 0.000 8 NA 0.011 0.001 6.99 NARu ppb 0.001 8 NA 0.002 0.001 60.9 NASb ppb 0.001 8 13.9 15.6 0.86 5.53 112Sc ppb 0.01 8 NA <0.01 --- na NASe ppb 3.0 8 5.49 5.22 2.74 52.5 95.1Sm ppb 0.000 8 NA 0.007 0.000 3.74 NASn ppb 0.006 8 NA 8.64 0.753 8.72 NASr ppb 0.01 8 190 218 11.8 5.44 115Ta ppb 0.001 8 NA 0.001 0.001 46.7 NATb ppb 0.000 8 NA 0.001 0.000 19.3 NATe ppb 0.001 8 NA 0.004 0.003 77.5 NATh ppb 0.000 8 NA 0.001 0.000 19.2 NATi ppb 0.01 8 NA 0.37 0.052 14 NATl ppb 0.000 8 13.8 11.9 1.18 9.88 86.6Tm ppb 0.000 8 NA 0.000 0.000 6.88 NAU ppb 0.000 8 5.04 5.12 0.348 6.8 102V ppb 0.000 8 14.4 15.9 1.85 11.7 110W ppb 0.001 8 NA 0.102 0.013 12.7 NAY ppb 0.000 8 NA 0.056 0.022 40.3 NA

Yb ppb 0.000 8 NA 0.003 0.000 5.76 NAZn ppb 0.4 8 19.2 26.1 2.45 9.38 136Zr ppb 0.001 8 NA 0.091 0.033 36.5 NA

Analysis of Analytical PrecisionHigh-Resolution ICP-MS Analysis of Water (Act Labs)based on USGS Standard Reference Material T-159

0

10

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Ag_

ppb

As_

ppb

Au_

ppb

B_p

pbB

a_pp

bB

e_pp

bB

i_pp

bC

a_pp

bC

d_pp

bC

e_pp

bC

o_pp

bC

r_pp

bC

s_pp

bC

u_pp

bD

y_pp

bE

r_pp

bE

u_pp

bFe

_ppb

Ga_

ppb

Gd_

ppb

Ge_

ppb

Hf_

ppb

Hg_

ppb

Ho_

ppb

In_p

pbK

_ppb

La_p

pbLi

_ppb

Lu_p

pbM

g_pp

bM

n_pp

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o_pp

bN

a_pp

bN

b_pp

bN

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bN

i_pp

bP

b_pp

bP

d_pp

bP

r_pp

bP

t_pp

bR

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bR

e_pp

bR

u_pp

bS

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bS

c_pp

bS

e_pp

bS

m_p

pbS

n_pp

bS

r_pp

bTa

_ppb

Tb_p

pbTe

_ppb

Th_p

pbTi

_ppb

Tl_p

pbTm

_ppb

U_p

pbV

_ppb

W_p

pbY

_ppb

Yb_

ppb

Zn_p

pbZr

_ppb

Elements

% R

SD


Figure 7-3. Precision plot for four analyses of standard reference material T–159 by High-Resolution ICP–MS. %RSD is percent relative standard deviation; RL is reporting limit.


Analysis of Analytical AccuracyHigh-Resolution ICP-MS Analysis of Water (Act Labs)Based on USGS Standard Reference Material T-159

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Ag_

ppb

As_

ppb

Au_

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B_p

pbB

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bB

i_pp

bC

a_pp

bC

d_pp

bC

e_pp

bC

o_pp

bC

r_pp

bC

s_pp

bC

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bD

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bE

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bFe

_ppb

Ga_

ppb

Gd_

ppb

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ppb

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Hg_

ppb

Ho_

ppb

In_p

pbK

_ppb

La_p

pbLi

_ppb

Lu_p

pbM

g_pp

bM

n_pp

bM

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bN

a_pp

bN

b_pp

bN

d_pp

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i_pp

bP

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bP

d_pp

bP

r_pp

bP

t_pp

bR

b_pp

bR

e_pp

bR

u_pp

bS

b_pp

bS

c_pp

bS

e_pp

bS

m_p

pbS

n_pp

bS

r_pp

bTa

_ppb

Tb_p

pbTe

_ppb

Th_p

pbTi

_ppb

Tl_p

pbTm

_ppb

U_p

pbV

_ppb

W_p

pbY

_ppb

Yb_

ppb

Zn_p

pbZr

_ppb

Elements

% R

ecov

ery


Figure 7-4. Accuracy plot for four analyses of standard reference material T–159 by High-Resolution ICP–MS. RL is reporting limit.





Ag ppb 0.002 8 0.1 0.002 0.000 19.8 2.01As ppb 0.04 8 3.3 6.82 3.47 50.9 207Au ppb 0.007 8 NA <0.007 NA NA NAB ppb 2.0 8 90.7 98.6 3.58 3.63 109Ba ppb 0.004 8 40.8 43.4 2.38 5.48 106Be ppb 0.001 8 1 1.26 0.039 3.1 126Bi ppb 0.000 8 NA 0.000 0.000 49.6 NACa ppb 0.005 8 31,400 32,600 2,170 6.65 104Cd ppb 0.000 8 2.5 3.04 0.334 11 122Ce ppb 0.002 8 NA 0.636 0.101 15.8 NACo ppb 0.001 8 2.6 2.65 0.202 7.62 102Cr ppb 0.006 8 8.5 9.07 0.32 3.53 107Cs ppb 0.001 8 NA 0.592 0.038 6.44 NACu ppb 0.01 8 7.8 8.02 0.72 8.98 103Dy ppb 0.000 8 NA 0.044 0.003 6.6 NAEr ppb 0.000 8 NA 0.035 0.005 15.3 NAEu ppb 0.000 8 NA 0.032 0.014 44.5 NAFe ppb 0.1 8 12.3 15.7 3.13 20 128Ga ppb 0.001 8 NA 0.010 0.003 33.5 NAGd ppb 0.000 8 NA 0.054 0.014 25.9 NA



Ge ppb 0.001 8 NA 0.030 0.013 43.6 NAHf ppb 0.000 8 NA 0.001 0.001 46.3 NAHg ppb 0.04 8 NA 0.049 0.025 51 NAHo ppb 0.000 8 NA 0.009 0.000 5.09 NAIn ppb 0.000 8 NA 0.004 0.001 15.6 NAK ppb 1.0 8 3,300 3,520 106 3.02 107La ppb 0.002 8 NA 0.5 0.086 17.2 NALi ppb 0.03 8 15.8 19.3 7.03 36.4 122Lu ppb 0.000 8 NA 0.003 0.000 7.89 NAMg ppb 0.2 8 7,630 8,270 554 6.71 108Mn ppb 0.1 8 346 353 16.4 4.66 102Mo ppb 0.004 8 4.12 3.8 0.278 7.3 92.3Na ppb 20 8 37,200 42,300 2,530 5.98 114Nb ppb 0.000 8 NA 0.001 0.000 37 NANd ppb 0.000 8 NA 0.398 0.034 8.49 NANi ppb 0.05 8 3.71 3.23 0.215 6.67 87Pb ppb 0.003 8 4.24 3.67 0.114 3.11 86.5Pd ppb 0.001 8 NA 0.092 0.015 16.3 NAPr ppb 0.000 8 NA 0.108 0.013 11.9 NAPt ppb 0.001 8 NA <0.001 NA NA NARb ppb 0.04 8 NA 8.19 0.574 7 NARe ppb 0.000 8 NA 0.031 0.002 5.5 NARu ppb 0.001 8 NA 0.002 0.001 61.4 NASb ppb 0.001 8 1.8 1.98 0.087 4.41 110Sc ppb 0.01 8 NA <0.01 NA NA NASe ppb 3.0 8 1.33 <3 NA NA 204Sm ppb 0.000 8 NA 0.069 0.004 6.33 NASn ppb 0.006 8 NA 1.1 0.109 9.87 NASr ppb 0.01 8 239 255 11.1 4.34 107Ta ppb 0.001 8 NA 0.001 0.000 38.3 NATb ppb 0.000 8 NA 0.017 0.005 33 NATe ppb 0.001 8 NA 0.003 0.002 71.6 NATh ppb 0.000 8 NA 0.001 0.001 90.6 NATi ppb 0.01 8 NA 0.378 0.076 20 NATl ppb 0.000 8 1.57 1.41 0.129 9.15 89.5

Tm ppb 0.000 8 NA 0.003 0.000 9.38 NAU ppb 0.000 8 1.76 1.78 0.163 9.18 101V ppb 0.000 8 1.18 1.32 0.164 12.5 111W ppb 0.001 8 NA 0.006 0.005 84.5 NAY ppb 0.000 8 NA 0.362 0.031 8.55 NA

Yb ppb 0.000 8 NA 0.023 0.002 7.92 NAZn ppb 0.4 8 304 421 38.6 9.17 138Zr ppb 0.001 8 NA 0.054 0.019 34.6 NA


Analysis of Analytical PrecisionHigh-Resolution ICP-MS Analysis of Water (Act Labs)based on USGS Standard Reference Material T-177

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U_p

pbV

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pbY

_ppb

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ppb

Zn_p

pbZr

_ppb

Elements

% R

SD


Figure 7-5. Precision plot for four analyses of standard reference material T–177 by High-Resolution ICP–MS. %RSD is percent relative standard deviation; RL is reporting limit.

Analysis of Analytical AccuracyHigh-Resolution ICP-MS Analysis of Water (Act Labs)Based on USGS Standard Reference Material T-177

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Ag_

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pbTe

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Tl_p

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Yb_

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Zn_p

pbZr

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Elements

% R

ecov

ery


Figure 7-6. Accuracy plot for four analyses of standard reference material T–177 by High-Resolution ICP–MS. RL is reporting limit.


Appendix 8: Quality Control Tables and Charts for Additional USGS Analytical Methods

Table 8-1. Summary statistics for assessing analytical variation on duplicate samples; determined for iron by ferrozine analysis and dissolved organic carbon (DOC) by combustion/infrared analysis of water samples at the USGS.




Fe total µg/L 0 4 45.2 237 101 5.45 5.38Fe (II) µg/L 5.0 4 20.7 202 76.5 12.8 16.7Fe (III) µg/L 0 4 9.4 57.5 25 7.79 31.2DOC mg/L 0.1 4 1.1 3.1 2.2 0.15 6.82

Analysis of Analytical PrecisionFe and DOC in Water by Various Methods (USGS Laboratories)


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SD

>5 x LDL<5 x LDLN/A15% RSD

Figure 8-1. Precision plot for four analytical duplicate sample pairs for iron by ferrozine analysis and dissolved organic carbon (DOC) by combustion/infrared analysis. %RSD is percent relative standard deviation; RL is reporting limit.

Appendix 8: Quality Control Tables and Charts for Additional USGS Analytical Methods 105

Table 8-2. Summary statistics for assessing analytical variation on duplicate samples pairs; determined on water samples by ion chromatography and titration at the USGS.




Cl– mg/L 0.04 9 0.1 2 1.31 0.12 9.17Fl– mg/L 0.08 5 0.08 0.4 0.175 0.063 36.2

NO3– mg/L 0.08 2 0.1 0.3 0.2 0.071 35.4

SO4-2 mg/L 0.02 9 1.3 46.6 9.87 0.193 1.95

Alkalinity mg/L 0.01 8 2.76 33.5 11.7 0.193 1.65

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Mean <5 x RL

Below RL

Control Limit

Analysis of Analytical PrecisionAnions and Alkalinity of Water (USGS Labs)


Figure 8-2. Precision plot for nine analytical duplicate sample pairs by ion chromatography and titration. %RSD is percent relative standard deviation; RL is reporting limit.


Table 8-3. Summary statistics for assessing analytical variation on the USGS standard reference material M–158; determined on waters samples by ion chromatography and titration at the USGS.




Cl– mg/L 0.04 6 90.7 91 0.589 0.648 100Fl– mg/L 0.08 6 0.5 0.422 0.072 17.1 84.3

NO3– mg/L 0.08 6 1.1 1.15 0.138 12 105

SO4-2 mg/L 0.02 6 105 106 1.13 1.07 101

Alkalinity mg/L 0.01 7 63.6 62.7 0.486 0.776 98.5

Analysis of Analytical PrecisionAnions and Alkalinity of Water (USGS Labs)

based on Standard Reference Material M-158

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_ppm

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SD


Figure 8-3. Precision plot for seven analyses of USGS standard reference material M–158 by ion chromatography and titration. %RSD is percent relative standard deviation; RL is reporting limit.

Appendix 8: Quality Control Tables and Charts for Additional USGS Analytical Methods 107

Analysis of Analytical AccuracyAnions and Alkalinity of Water (USGS Labs)

based on Standard Reference Material M-158

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Figure 8-4. Accuracy plot for seven analyses of USGS standard reference material M–158 by ion chromatography and titration. RL is reporting limit.

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