EPA/600/4-90/023
September 1990
HANDBOOK OF METHODS FOR ACID DEPOSITION STUDIES
LABORATORY ANALYSES FOR SOIL CHEMISTRY
by
Blume, L.J., B.A. Schumacher, P.W. Schaffer, K.A. Cappo, M.L. Papp,
R.D. Van Remortel, D.S. Coffey, M.G. Johnson, and D.J. Chaloud
A Contribution to the
National Acid Precipitation Assessment Program
U.S.
,; 'L'V/0
U.S. Environmental Protection Agency
Office of Modeling, Monitoring Systems, and Quality Assurance
Office of Ecological Processes and Effects Research
Office of Research and Development
Washington, D.C. 20460
Environmental Monitoring Systems Laboratory, Las Vegas, Nevada 89193
Environmental Research Laboratory, Corvallls, Oregon 97333
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Notice
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Notice
The information in this document has been funded wholly or in part by the U.S. Environmental
Protection Agency under contract number 68-03-3249 to Lockheed Engineering & Sciences Company.
It has been subject to the Agency's peer and administrative review, and it has been approved for
publication as an Agency document.
Mention of corporation names, trade names, or commercial products does not constitute
endorsement or recommendation for use.
This document is a contribution to the National Acid Precipitation Assessment Program. The
methods described in this document have been developed for use in the component programs of
the Aquatic Effects Research Program.
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Abstract
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Abstract
This handbook describes methods used to process and analyze soil samples. It is intended
as a guidance document for groups involved in acid deposition monitoring activities similar to those
implemented by the U.S. Environmental Protection Agency's Aquatic Effects Research Program, a
part of the National Acid Precipitation Assessment Program. These methods were developed for
use in the Direct/Delayed Response Project, a component project of the Aquatic Effects Research
Program within the Office of Ecological Processes and Effects Research. This program addresses
the following issues relating to the effects of acid deposition on aquatic ecosystems:
• The extent and magnitude of past change.
• The change to be expected in the future under various deposition scenarios.
• The maximum rates of deposition below which further change is not expected.
• The rate of change or recovery of aquatic ecosystems if deposition rates are decreased.
The following chemical and physical parameters were measured during the Direct/Delayed
Response Project and are described in this document.
• Percent fine gravel
• Percent medium gravel
• Bulk density-clod
• Bulk density-known volume
• Field-moist pH
• loss-on-ignition (percent organic matter)
• Soil moisture
• Percent total sand
• Percent very coarse sand
• Percent coarse sand
• Percent medium sand
• Percent fine sand
• Percent very fine sand
• Percent total silt
• Percent coarse silt
• Percent fine silt
• Percent total clay
• pH in deionized water
• pH in 0.002 M calcium chloride
• pH in 0.01 M calcium chloride
• Cation exchange capacity (ammonium chloride
saturating solution)
• Cation exchange capacity (ammonium acetate
saturating solution)
• Calcium, exchangeable in ammonium acetate
• Magnesium, exchangeable in ammonium acetate
• Potassium, exchangeable in ammonium acetate
• Sodium, exchangeable in ammonium acetate
• Calcium, exchangeable in ammonium chloride
• Magnesium, exchangeable in ammonium chloride
• Potassium, exchangeable in ammonium chloride
• Sodium, exchangeable in ammonium chloride
• Aluminum, exchangeable in ammonium chloride
• Calcium, exchangeable in calcium chloride
• Magnesium, exchangeable in calcium chloride
• Potassium, exchangeable in calcium chloride
• Sodium, exchangeable in calcium chloride
• Iron, exchangeable in calcium chloride
• Aluminum, exchangeable in calcium chloride
• Exchangeable acidity in barium chloride
• Iron, extractable in pyrophosphate
• Aluminum, extractable in pyrophosphate
• Iron, extractable in acid-oxalate
• Aluminum, extractable in acid-oxalate
• Silicon, extractable in acid-oxalate
• Iron, extractable in citrate-dithionite
• Aluminum, extractable in citrate-dithionite
• Sulfate, extractable in deionized water
• Sulfate, extractable in sodium phosphate
• Sulfate, 0 mg S/L isotherm
• Sulfate, 2 mg S/L isotherm
• Sulfate, 4 mg S/L isotherm
• Sulfate, 8 mg S/L isotherm
• Sulfate, 16 mg S/L isotherm
• Sulfate, 32 mg S/L isotherm
• Total carbon
• Total nitrogen
• Total sulfur
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Abstract
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Page 2 of 2
This handbook was submitted in fulfillment of Contract Number 68-03-3249 by Lockheed
Engineering & Sciences Company under the sponsorship of the U.S Environmental Protection Agency.
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Contents
Section Page Revision
Notice 1 of 1 0
Abstract 1 of 5 0
Figures 1 of 1 0
Tables 1 of 1 0
Glossary 1 of 5 0
Acknowledgments 1 of 3 0
1.0 Introduction 1 of 14 0
1.1 AERP Handbooks 1 of 14 0
1.1.1 Types of Handbooks 1 of 14 0
1.1.2 Structure of Volumes 1 of 14 0
1.1.3 Interrelationship of Volumes 1 of 14 0
1.2 Content of Laboratory Analyses Handbook 1 of 14 0
1.3 Overview of the DDRP 9 of 14 0
1.4 References 10 of 14 0
2.0 Preparation Laboratory Facilities and Organization 1 of 4 0
2.1 Facilities Requirements 1 of 4 0
2.2 Staffing 2 of 4 0
2.3 Training 3 of 4 0
2.4 Safety 3 of 4 0
2.5 References 4 of 4 0
3.0 General Laboratory Procedures 1 of 20 0
3.1 Sample Handling 1 of 20 0
3.1.1 Preparation Laboratory Sample Receipt and Tracking 1 of 20 0
3.1.2 Analytical Laboratory Sample Receipt and Tracking 3 of 20 0
3.2 Quality Control 4 of 20 0
3.2.1 Instrument Detection Limits 4 of 20 0
3.2.2 Calibration and Standardization 4 of 20 0
3.2.3 Blanks 16 of 20 0
3.2.4 Replicate Sample Analysis 16 of 20 0
3.2.5 Quality Control Standards 18 of 20 0
3.2.6 Matrix Spikes 18 of 20 0
3.2.7 Ion Chromatography Resolution 19 of 20 0
3.2.8 Quality Control Audit Sample 19 of 20 0
3.3 Data Entry and Record Keeping 19 of 20 0
3.3.1 Raw Data 19 of 20 0
3.3.2 Reported Data 19 of 20 0
3.4 References 20 of 20 0
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Contents (Continued)
Section Page Revision
4.0 Sample Processing and Rock Fragment Determination 1 of 7 0
4.1 Overview 1 of 7 0
4.1.1 Summary of Method 1 of 7 0
4.1.2 Interferences 2 of 7 0
4.1.3 Safety 2 of 7 0
4.2 Sample Collection. Preservation, and Storage 2 of 7 0
4.3 Equipment and Supplies 2 of 7 0
4.3.1 Equipment Specifications 2 of 7 0
4.3.2 Apparatus 3 of 7 0
4.3.3 Reagents and Consumable Materials 3 of 7 0
4.4 Calibration and Standardization 4 of 7 0
4.5 Quality Control 4 of 7 0
4.6 Procedure 4 of 7 0
4.6.1 Sample Drying 4 of 7 0
4.6.2 Disaggregation and Sieving 5 of 7 0
4.6.3 Homogenization and Subsampling (Preparation Laboratory) . . 5 of 7 0
4.6.4 Homogenization and Subsampling (Analytical Laboratory) .... 6 of 7 0
4.6.5 Rock Fragment Determination 7 of 7 0
4.7 Percent Rock Fragment Calculations 7 of 7 0
4.8 References 7 of 7 0
5.0 Bulk Density Determination 1 of 10 0
5.1 Overview 1 of 10 0
5.1.1 Summary of Method 1 of 10 0
5.1.2 Interferences 1 of 10 0
5.1.3 Safety 1 of 10 0
5.2 Sample Collection, Preservation, and Storage 2 of 10 0
5.3 Equipment and Supplies 2 of 10 0
5.3.1 Apparatus 2 of 10 0
5.3.2 Reagents 4 of 10 0
5.3.3 Consumable Materials 5 of 10 0
5.4 Calibration and Standardization 5 of 10 0
5.5 Quality Control 5 of 10 0
5.6 Procedure 5 of 10 0
5.6.1 Clod Method 5 of 10 0
5.6.2 Known Volume Method 7 of 10 0
5.7 Calculations 7 of 10 0
5.7.1 Clod Method 7 of 10 0
5.7.2 Known Volume Method 9 of 10 0
5.8 References 9 of 10 0
6.0 Field-Moist pH Determination 1 of 8 0
6.1 Overview 1 of 8 0
6.1.1 Scope and Application 1 of 8 0
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Contents (Continued}
Section Page Revision
6.1.2 Summary of Method 1 of 8 0
6.1.3 Interferences 1 of 8 0
6.1.4 Safety 2 of 8 0
6.2 Sample Collection, Preservation, and Storage 2 of 8 0
6.3 Equipment and Supplies 2 of 8 0
6.3.1 Equipment Specifications 2 of 8 0
6.3.2 Apparatus, Consumable Materials, and Reagents 2 of 8 0
6.4 Calibration and Standardization 3 of 8 0
6.4.1 Instrument Preparation 3 of 8 0
6.4.2 Calibration with Buffers 4 of 8 0
6.4.3 Maintenance 5 of 8 0
6.4.4 pH Meter Electronic Checkout '. 5 of 8 0
6.4.5 Electrode Etching Procedure 5 of 8 0
6.5 Quality Control 6 of 8 0
6.5.1 Initial Quality Control Check 6 of 8 0
6.5.2 Routine Quality Control Checks 6 of 8 0
6.5.3 Quality Control/Quality Evaluation Samples 7 of 8 0
6.6 Procedure 7 of 8 0
6.6.1 Sample Preparation 7 of 8 0
6.6.2 Sample Measurement 7 of 8 0
6.6.3 Cleanup 8 of 8 0
6.7 Calculations 8 of 8 0
6.8 References 8 of 8 0
7.0 Organic Matter Determination by Loss-On-Ignition 1 of 3 0
7.1 Overview 1 of 3 0
7.1.1 Summary of Method 1 of 3 0
7.1.2 Interferences 1 of 3 0
7.1.3 Safety 1 of 3 0
7.2 Sample Collection, Preservation, and Storage 1 of 3 0
7.3 Equipment and Supplies 1 of 3 0
7.3.1 Apparatus 1 of 3 0
7.3.2 Consumable Materials 2 of 3 0
7.4 Calibration and Standardization 2 of 3 0
7.5 Quality Control 2 of 3 0
7.6 Procedure 2 of 3 0
7.7 Calculations 3 of 3 0
7.8 References 3 of 3 0
8.0 Air-Dry Moisture Determination 1 of 4 0
8.1 Overview 1 of 4 0
8.1.1 Summary of Method 1 of 4 0
8.1.2 Interferences 1 of 4 0
8.1.3 Safety 1 of 4 0
8.2 Sample Collection, Preservation, and Storage 1 of 4 0
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Contents (Continued)
Section Page Revision
8.3 Equipment and Supplies 1 of 4 0
8.3.1 Apparatus 1 of 4 0
8.3.2 Consumable Materials 2 of 4 0
8.4 Calibration and Standardization 2 of 4 0
8.5 Quality Control 2 of 4 0
8.6 Procedure 2 of 4 0
8.6.1 Preparation Laboratory 2 of 4 0
8.6.2 Analytical Laboratory 3 of 4 0
8.7 Calculations 3 of 4 0
8.7.1 Preparation Laboratory 3 of 4 0
8.7.2 Analytical Laboratory 4 of 4 0
8.8 References 4 of 4 0
9.0 Particle Size Analysis 1 of 8 0
9.1 Overview 1 of 8 0
9.1.1 Summary of Method 1 of 8 0
9.1.2 Interferences 1 of 8 0
9.1.3 Safety 1 of 8 0
9.2 Sample Collection, Preservation, and Storage 1 of 8 0
9.3 Equipment and Supplies 1 of 8 0
9.3.1 Apparatus 1 of 8 0
9.3.2 Reagents and Consumable Materials 3 of 8 0
9.4 Calibration and Standardization 3 of 8 0
9.5 Quality Control 3 of 8 0
9.6 Procedure 4 of 8 0
9.6.1 Removing Organic Matter 4 of 8 0
9.6.2 Separating Sand from Silt and Clay 5 of 8 0
9.6.3 Sieving and Weighing the Sand Fractions 5 of 8 0
9.6.4 Pipetting 5 of 8 0
9.7 Calculations 7 of 8 0
9.7.1 Input (raw data) 7 of 8 0
9.7.2 Calculated Data 8 of 8 0
9.8 References 8 of 8 0
10.0 pH Determination 1 of 7 0
10.1 Overview 1 of 7 0
10.1.1 Scope and Application 1 of 7 0
10.1.2 Summary of Method 1 of 7 0
10.1.3 Interferences 1 of 7 0
10.1.4 Safety 2 of 7 0
10.2 Sample Collection, Preservation, and Storage 2 of 7 0
10.3 Equipment and Supplies 2 of 7 0
10.3.1 Equipment Specifications 2 of 7 0
10.3.2 Reagents 2 of 7 0
10.3.3 Consumable Materials 3 of 7 0
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Contents (Continued)
Section Page Revision
10.4 Calibration and Standardization 3 of 7 0
10.4.1 Instrument Preparation 3 of 7 0
10.4.2 Calibration with Buffers 4 of 7 0
10.4.3 Maintenance 4 of 7 0
10.4.4 pH Meter Electronic Checkout 5 of 7 0
10.4.5 Electrode Etching Procedure 6 of 7 0
10.5 Quality Control 6 of 7 0
10.6 Procedure 6 of 7 0
10.6.1 Preparing Soil Suspensions 6 of 7 0
10.6.2 pH Measurements 7 of 7 0
10.7 Calculations 7 of 7 0
10.8 References 7 of 7 0
11.0 Cation Exchange Capacity 1 of 12 0
11.1 Overview 1 of 12 0
11.1.1 Scope and Application 1 of 12 0
11.1.2 Summary of Method 1 of 12 0
11.1.3 Interferences 1 of 12 0
11.1.4 Safety 2 of 12 0
11.2 Sample Collection, Preservation, and Storage 2 of 12 0
11.3 Equipment and Supplies 2 of 12 0
11.3.1 Apparatus for Saturation Procedure 2 of 12 0
11.3.2 Apparatus for Analysis 2 of 12 0
11.3.3 Reagents and Consumable Materials for
Saturation Procedure 4 of 12 0
11.3.4 Reagents and Consumable Materials for Analysis 5 of 12 0
11.4 Calibration and Standardization 7 of 12 0
11.4.1 Flow Injection Analysis Calibration 7 of 12 0
11.4.2 Titration Calibration 7 of 12 0
11.5 Quality Control 7 of 12 0
11.6 Procedure 8 of 12 0
11.6.1 Pulp Washing 8 of 12 0
11.6.2 Extraction 9 of 12 0
11.6.3 Analytical Procedure using FIA 10 of 12 0
11.6.4 Analytical Procedure using Automated
Distillation-Titration 10 of 12 0
11.6.5 Analytical Procedure using Manual Distillation-
Automated Titration 11 of 12 0
11.7 Calculations 11 of 12 0
11.7.1 Flow Injection Analysis 11 of 12 0
11.7.2 Titration 11 of 12 0
11.8 References 12 of 12 0
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Contents (Continued)
Section Page Revision
12.0 Exchangeable Cations in Ammonium Acetate 1 of 9 0
12.1 Overview 1 of 9 0
12.1.1 Summary of Method 1 of 9 0
12.1.2 Interferences 2 of 9 0
12.1.3 Safety 2 of 9 0
12.2 Sample Collection, Preservation, and Storage 2 of 9 0
12.3 Equipment and Supplies 2 of 9 0
12.3.1 Equipment Specifications 2 of 9 0
12.3.2 Reagents and Consumable Materials 3 of 9 0
12.4 Calibration and Standardization 6 of 9 0
12.5 Quality Control 6 of 9 0
12.6 Procedure 7 of 9 0
12.6.1 Procedure for Determinations by Atomic Absorption 7 of 9 0
12.6.2 Procedure for Determinations by Inductively
Coupled Plasma 8 of 9 0
12.6.3 Procedure for Determinations by Emission
Spectroscopy 8 of 9 0
12.7 Calculations 9 of 9 0
12.8 References 9 of 9 0
13.0 Exchangeable Cations in Ammonium Chloride 1 of 9 0
13.1 Overview 1 of 9 0
13.1.1 Summary of Method 1 of 9 0
13.1.2 Interferences 2 of 9 0
13.1.3 Safety 2 of 9 0
13.2 Sample Collection, Preservation, and Storage 2 of 9 0
13.3 Equipment and Supplies 3 of 9 0
13.3.1 Equipment Specifications 3 of 9 0
13.3.2 Reagents and Consumable Materials 3 of 9 0
13.4 Calibration and Standardization 6 of 9 0
13.5 Quality Control 6 of 9 0
13.6 Procedure 7 of 9 0
13.6.1 Procedure for Determinations by Atomic Absorption 7 of 9 0
13.6.2 Procedure for Determinations by Inductively
Coupled Plasma 8 of 9 0
13.6.3 Procedure for Determination by Emission
Spectroscopy 8 of 9 0
13.7 Calculations 9 of 9 0
13.8 References 9 of 9 0
14.0 Exchangeable Cations in Calcium Chloride for Lime and
Aluminum Potential 1 of 8 0
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Contents (Continued)
Section Page Revision
14.1 Overview 1 of 8 0
14.1.1 Summary of Method 1 of 8 0
14.1.2 Interferences 2 of 8 0
14.1.3 Safety 2 of 8 0
14.2 Sample Collection, Preservation, and Storage 3 of 8 0
14.3 Equipment and Supplies 3 of 8 0
14.3.1 Equipment Specifications 3 of 8 0
14.3.2 Apparatus 3 of 8 0
14.3.3 Reagents and Consumable Materials 4 of 8 0
14.4 Calibration and Standardization 4 of 8 0
14.5 Quality Control 4 of 8 0
14.6 Procedure 6 of 8 0
14.6.1 Extraction 6 of 8 0
14.6.2 Cation Determination 6 of 8 0
14.6.3 pH Determination 7 of 8 0
14.7 Calculations 7 of 8 0
14.8 References 8 of 8 0
15.0 Exchangeable Acidity 1 of 6 0
15.1 Overview 1 of 6 0
15.1.1 Summary of Method 1 of 6 0
15.1.2 Interferences 1 of 6 0
15.1.3 Safety 1 of 6 0
15.2 Sample Collection, Preservation, and Storage 1 of 6 0
15.3 Equipment and Supplies 1 of 6 0
15.3.1 Apparatus and Equipment 1 of 6 0
15.3.2 Reagents 2 of 6 0
15.3.3 Consumable Materials 3 of 6 0
15.4 Calibration and Standardization 3 of 6 0
15.5 Quality Control 3 of 6 0
15.6 Procedure 4 of 6 0
15.6.1 Mineral Soils 4 of 6 0
15.6.2 Organic Soils 5 of 6 0
15.7 Calculations 6 of 6 0
15.8 References 6 of 6 0
16.0 Extractable Iron, Aluminum, and Silicon 1 of 8 0
16.1 Overview 1 of 8 0
16.1.1 Summary of Method 1 of 8 0
16.1.2 Interferences 1 of 8 0
16.1.3 Safety 2 of 8 0
16.2 Sample Collection, Preservation, and Storage : 2 of 8 0
16.3 Equipment and Supplies 2 of 8 0
16.3.1 Equipment Specifications 2 of 8 0
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Contents (Continued)
Section Page Revision
16.3.2 Apparatus 2 of 8 0
16.3.3 Reagents 3 of 8 0
16.3.4 Consumable Materials 4 of 8 0
16.4 Calibration and Standardization 4 of 8 0
16.5 Quality Control 5 of 8 0
16.6 Procedure 5 of 8 0
16.6.1 Sodium Pyrophosphate Extraction 6 of 8 0
16.6.2 Acid-Oxalate Extraction 6 of 8 0
16.6.3 Citrate-Dithionite Extraction 7 of 8 0
16.7 Calculations 7 of 8 0
16.8 References 8 of 8 0
17.0 Extractable Sulfate 1 of 8 0
17.1 Overview 1 of 8 0
17.1.1 Summary of Method 1 of 8 0
17.1.2 Interferences 1 of 8 0
17.1.3 Safety 2 of 8 0
17.2 Sample Collection, Preservation, and Storage 2 of 8 0
17.3 Equipment and Supplies 2 of 8 0
17.3.1 Equipment Specifications 2 of 8 0
17.3.2 Apparatus 2 of 8 0
17.3.3 Reagents 3 of 8 0
17.3.4 Consumable Materials 3 of 8 0
17.4 Calibration and Standardization 4 of 8 0
17.4.1 Water Extract 4 of 8 0
17.4.2 Phosphate Extract 4 of 8 0
17.5 Quality Control 4 of 8 0
17.6 Procedure 5 of 8 0
17.6.1 Extraction of Sulfate by Deionized Water 5 of 8 0
17.6.2 Extraction of Sulfate by Sodium Phosphate
(NaH/OJ Solution 6 of 8 0
17.6.3 Determination of Sulfate by Ion Chromatography 6 of 8 0
17.7 Calculations 7 of 8 0
17.8 References 8 of 8 0
18.0 Sulfate Adsorption Isotherms 1 of 7 0
18.1 Overview 1 of 7 0
18.1.1 Scope and Application 1 of 7 0
18.1.2 Summary of Method 1 of 7 0
18.1.3 Interferences 1 of 7 0
18.1.4 Safety 2 of 7 0
18.2 Sample Collection, Preservation, and Storage 2 of 7 0
18.3 Equipment and Supplies 2 of 7 0
18.3.1 Equipment Specifications 2 of 7 0
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Contents (Continued)
Section Page Revision
18.3.2 Apparatus 2 of 7 0
18.3.3 Reagents and Consumable Materials 3 of 7 0
18.4 Calibration and Standardization 3 of 7 0
18.5 Quality Control 3 of 7 0
18.6 Procedure 4 of 7 0
18.6.1 Sample Preparation 5 of 7 0
18.6.2 Determination of Sulfate by Ion Chromatography 5 of 7 0
18.7 Calculations 7 of 7 0
18.8 References 7 of 7 0
19.0 Total Carbon and Nitrogen 1 of 4 0
19.1 Overview 1 of 4 0
19.1.1 Summary of Method 1 of 4 0
19.1.2 Interferences 1 of 4 0
19.1.3 Safety 1 of 4 0
19.2 Sample Collection, Preservation, and Storage 2 of 4 0
19.3 Equipment and Supplies 2 of 4 0
19.3.1 Apparatus and Equipment 2 of 4 0
19.3.2 Reagents and Consumable Materials 2 of 4 0
19.4 Calibration and Standardization 2 of 4 0
19.5 Quality Control 3 of 4 0
19.6 Analytical Procedures 4 of 4 0
19.7 Calculations 4 of 4 0
19.8 References 4 of 4 0
20.0 Total Sulfur 1 of 5 0
20.1 Overview 1 of 5 0
20.1.1 Summary of Method 1 of 5 0
20.1.2 Interferences 1 of 5 0
20.1.3 Safety 1 of 5 0
20.2 Sample Collection, Preservation, and Storage 1 of 5 0
20.3 Equipment and Supplies 2 of 5 0
20.3.1 Apparatus and Equipment 2 of 5 0
20.3.2 Reagents and Consumable Materials 2 of 5 0
20.4 Calibration and Standardization 2 of 5 0
20.5 Quality Control 3 of 5 0
20.6 Analytical Procedures 4 of 5 0
20.7 Calculations 4 of 5 0
20.8 References 5 of 5 0
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Appendices
Appendix A - General Laboratory Procedures 1 of 4 0
Appendix B - Direct/Delayed Response Project Blank Data Form 1 of 103 0
Appendix C - Atomic Absorption Spectroscopy Methods 1 of 19 0
Appendix D - Inductively Coupled Plasma Atomic Emission Spectrometric
Method for Trace Element Analyses of Water and Wastes 1 of 12 0
Appendix E - Emission Spectroscopy Methods 1 of 12 0
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Figures
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Figures
Section Page Revision
3-1 DDRP Label A 1 of 20 0
3-2 DDRP Label B 3 of 20 0
11-1 Mechanical Extractor 3 of 12 0
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Tables
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Tables
Section Page Revision
1-1 Parameter Descriptions and Codes 2 of 14 0
2-1 Preparation Laboratory Supplies 1 of 4 0
3-1 Summary of Internal Quality Control 5 of 20 0
3-2 Contract-Required Detection Limits, Reporting Units,
and Expected Ranges 15 of 20 0
3-3 Intralaboratory Precision Goals for Laboratory Replicates 17 of 20 0
3-4 Analytical Laboratory Data Qualifiers (Tags) 19 of 20 0
5-1 Density of Pure Water 8 of 10 0
6-1 pH Values of Buffers at Various Temperatures 4 of 8 0
9-1 Sedimentation Times for Fine Silt and Clay Particles Settling
Through Water to a Depth of Ten Centimeters 6 of 8 0
9-2 Sedimentation Times and Pipetting Depths for Clay Particles 7 of 8 0
10-1 pH Values of Buffers at Various Temperatures 5 of 7 0
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Glossary
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Page 1 of 5
Glossary
I. Definitions
degree of agreement of a measurement with an accepted or true value. As used here,
accuracy is determined from the difference between recorded measurements and accepted true
values of audit samples and calibration standards. Accuracy is generally expressed as percent bias.
Aliquot--t< portion of sample treated (processed) in a specific way for a particular parameter or set
of parameters.
Audit sample-k material with known characteristics which is used to determine the accuracy of the
measurement system. In the Aquatic Effects Research Program (AERP) studies, natural media
samples, prepared matrices, and certified (purchased) audit samples are employed.
Base safurat/on-The sum of exchangeable base cations divided by the cation exchange capacity;
expressed as a percentage.
Batch-M\ samples, including routine, duplicate or replicate, blank, and audit samples, that are
processed together at a single laboratory on a single day.
fl/as--A systematic difference between repeated measurements and an accepted or true value.
Blank samp/e-Two different blank samples are referenced in these methods:
1. Calibration blank - A 0 mg/L standard that contains only the matrix of the calibration
standards. The measured concentration should be less than or equal to the contract-
required detection limit.
2. Reagent blank - A reagent blank contains all of the reagents (in the same quantities) used
in preparing a regular sample for analysis. It is processed in the same manner as a
regular sample. The measured concentration should be less than or equal to the contract-
required detection limit.
Bulk density--J\n& weight of dry soil per unit volume including pore space; expressed in g/cm3.
Bulk sample-Soft samples taken from a designated portion of a specific horizon. As used here, the
bulk sample is approximately 1 gallon of soil that weighs approximately 5.5 kilograms. All analyses
except bulk density are performed on aliquots prepared from the bulk sample.
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Glossary
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Confidence Interval--^ value interval that has a designated probability of including some defined
parameter of the population.
Detection limit (also instrument detection limit or IDLJ~Ttvee times the standard deviation of at least
15 nonconsecutive calibration blank or detection limit quality control check sample analyses run on
at least three separate days.
Duplicate--^ second, independent determination of the same sample, performed by the same
analyst, at essentially the same time and under the same conditions.
Exchangeable acidity-Tbe total hydrogen ions held on soil colloids or organic matter (reserve acidity)
plus those ions present in the soil solution (active acidity); expressed in milliequivalents per 100
grams of soil.
Known volume samples-Soft samples of a specific volume taken from horizons which fail to yield
satisfactory clod samples; used to determine bulk density.
Matrix spike sa/np/e--Addition of a known amount of analyte (spike) to a sample portion; used to
investigate chemical and matrix interferences. The spike should be approximately equal to the
endogenous level or ten times the detection limit, whichever is larger.
NBS-traceable-k material or instrument which is certified against a National Bureau of Standards
primary standard.
NOTE: The National Bureau of Standards is now the National Institute of Standards and
Technology; however, NBS-traceable is still the appropriate designation for standards
certified prior to the name change.
jDeoto/7--The smallest three-dimensional body of soil that is recognizable as a soil individual. The
lateral dimensions are generally considered to be 1-10 m2 which permits the study of the nature of
all horizons present in the soil.
Percent relative standard deviation (%RSD)—1\\Q standard coefficient of variation, calculated by:
s
%RSD = x 100
X
where :
s = standard deviation
X = mean of recorded measurements
p/y-The negative logarithm of the activity of hydrogen ions; expressed in pH units.
Precision~~ft\Q mutual agreement among individual measurements of the same property. As used
here, precision is calculated from results of duplicate analyses and repetitive analyses of audit
samples and quality control check solutions. Precision is generally expressed in terms of percent
relative standard deviation.
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Glossary
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Preparation laboratory--!^ used here, a separate facility intermediate to field activities and analytical
laboratories. The primary function of the preparation laboratory is to create sample batches,
incorporating quality evaluation/quality control samples in such a way as to make them unknown
(blind) to the analytical laboratory analysts. Additional functions of the preparation laboratory
include sample processing, performance of a limited number of sample analyses, and logistical
support of field activities.
Quality assurance-The overall system used to ensure that the quality control system is performing.
Quality contro/~The specific procedures and checks used to provide a quality product.
Quality control check sample (QCCS)--k known sample containing the analyte of interest at a
concentration in the low- to mid-calibration range. Whenever possible, the QCCS should be
prepared from a source independent of that used to prepare calibration standards.
Quality evaluation samp/es-see Audit sample.
Standard additions--^ method of analysis in which equal volumes of a sample are added to a
deionized water blank and to three standards containing different known amounts of the test
element. Standard additions are used when matrix or chemical interferences are present.
Standard dev/at/on-The square root of the variance of a set of values.
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II. Acronyms
Glossary
Revision 0
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Page 4 of 5
AA
ACS
ADS
ADDNET
AERP
APHA
ASTM
BaCI2-TEA
CEC
CHN
CPR
CRDL
DDRP
DI
DL-QCCS
EPA
ES
FIA
1C
ICP
ID
IDL
IR
LDR
LPE
LOI
MASS
meq
mV
NAPAP
NBS
NCASI
NSWS
OSHA
%RSD
PVC
QA
QC
QCAS
atomic absorption spectrometry
American Chemical Society
Acid Deposition System
Acid Deposition Data Network
Aquatic Effects Research Program
American Public Health Association
American Society for Testing and Materials
barium chloride triethanolamine
cation exchange capacity
carbon-hydrogen-nitrogen
cardio-pulmonary resuscitation
contract-required detection limit
Direct/Delayed Response Project
deionized
detection limit quality control check sample
U.S. Environmental Protection Agency
emission spectroscopy
flow injection analyzer
ion chromatography
inductively coupled plasma
identification
instrument detection limit
infrared
• linear dynamic range
linear polyethylene
loss-on-ignition
Mid-Appalachian Soil Survey
milliequivalents
millivolt
National Acid Precipitation Assessment Program
National Bureau of Standards (now National Institute of Standards and
Technology)
National Council of Paper Industry for Air and Stream Improvement
National Surface Water Survey
Occupational Safety & Health Administration
percent relative standard deviation
polyvinyl chloride
quality assurance
quality control
QC audit sample
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Page 5 of 5
II. Acronyms (Continued)
QCCS QC check sample
QE quality evaluation
RF radio frequency
SCS Soil Conservation Service
SRM standard reference material
USDA/SCS U.S. Department of Agriculture/Soil Conservation Service
VF volume filling
VR volume replacement
III. Measurement Symbols
o
C degrees Centigrade
cm centimeter, 10 m
cm3 cubic centimeter
g gram
hr hour
*K degrees Kelvin
kg kilogram, 103g
L liter
M molar
m meter
meq milliequivalent
mg milligram
min. minute
mL milliliter, 10'3 L
mm millimeter, 10"3 m
mV millivolt, 10"3 volt
N normality
nm nanometer, 10"8 m
(Jig microgram, 10"8 g
fjL microliter, 10"8 L
micron, 10"* m
micron Siemens per centimeter
v/v volume to volume
w/v weight to volume
< less than
% percent
± plus or minus
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Ad
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Actoowtedgrnents
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Page 2 of 3
• Oak Ridge National Laboratory
R. S. Turner
• Soil Conservation Service
L. Juve (retired), F. M. Kaisaki, and L Shields (retired)
• Huffman Laboratory
N. Fish, R. N. Heistand, E. Huffman, and D. Raines
• Weyerhauster Laboratories
K. Doxsee and T. Frost
• Harris Laboratories
T. Buet and K. Shields
• University of Nebraska at Lincoln
J. Den and D. Knudsen
• University of Maine
I. Fernandez
Aquatic Effects Research Program documents which contributed directly to evolution of the
methods and, hence, to the development of this handbook include:
Anon. 1988. Invitation for Bid on Solicitation # W802498D1. Internal Report. U.S. Environmental
Protection Agency, Environmental Monitoring Systems Laboratory, Las Vegas, Nevada. 454
PP-
Bartling, M. H., M. L. Papp, and R. D. Van Remortel. 1988. Direct/Delayed Response Project:
Preparation Laboratory Standard Operating Procedures for the Mid-Appalachian Soil Survey.
Internal Report. U.S. Environmental Protection Agency, Environmental Monitoring Systems
Laboratory. Las Vegas, Nevada. 61 pp.
Cappo, K., L J. Blume, G. A. Raab, J. K. Bartz, and J. L. Engels. 1987. Direct/Delayed Response
Project: Analytical Methods Manual for the Mid-Appalachian Soil Survey. EPA/600/8-87/020.
U.S. Environmental Protection Agency, Environmental Monitoring Systems Laboratory, Las
Vegas, Nevada. 318 pp.
Cappo, K. A., L J. Blume, G. A. Raab, J. K. Bartz, and J. L. Engels. 1987. Analytical Methods Manual
for Direct/Delayed Response Project Soil Survey. EPA/600/8-87/020. U.S. Environmental
Protection Agency, Office of Research and Development, Las Vegas, Nevada. 318 pp.
Coffey, D. S., M. L Papp, J. K. Bartz, R. D. Van Remortel, J. J. Lee, D. A. Lammers, M. G. Johnson,
and G. R. Holdren. 1987. Direct/Delayed Response Project: Field Operations and Quality
Assurance Report for Soil Sampling and Preparation in the Northeastern U.S. Volume I: Soil
Sampling. EPA 600/4-87/030. U.S. Environmental Protection Agency, Environmental Monitoring
Systems Laboratory, Las Vegas, Nevada. 193 pp.
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Ackwwlecgrnents
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Page 3 of 3
Coffey, D. S., J. J. Lee, J. K. Bartz, R. D. Van Remortel, M. L. Papp, and G. R. Holdren. 1987.
Direct/Delayed Response Project: Field Operations and Quality Assurance Report for Soil
Sampling and Preparation in the Southern Blue Ridge Province. Volume I: Sampling. EPA
600/4-87/041. U.S. Environmental Protection Agency, Environmental Monitoring Systems
Laboratory, Las Vegas, Nevada. 205 pp.
Haren, M. and R. D. Van Remortel. 1987. Direct/Delayed Response Project: Field Operations and
Quality Assurance Report for Soil Sampling and Preparation in the Southern Blue Ridge
Province of the U.S. Volume II: Preparation. EPA 600/4-87/041. U.S. Environmental Protection
Agency, Environmental Monitoring Systems Laboratory, Las Vegas, Nevada. 28 pp.
Papp, M. L and R. D. Van Remortel. 1990. Direct/Delayed Response Project: Preparation
Laboratory Operations and Quality Assurance Report for the Mid-Appalachian Soil Survey.
EPA/600/4-90/017. U.S. Environmental Protection Agency, Environmental Monitoring Systems
Laboratory, Las Vegas, Nevada. 183 pp.
Papp, M. L. and R. D. Van Remortel. 1988. Direct/Delayed Response Project: Preparation
Laboratory Standard Operating Procedures for the Mid-Appalachian Soil Survey. Internal
Report. U.S. Environmental Protection Agency, Environmental Monitoring Systems Laboratory,
Las Vegas, Nevada. 61 pp.
Papp, M. L and R. D. Van Remortel. 1987. Direct/Delayed Response Project: Field Operations and
Quality Control for Soil Sampling and Preparation in the Northeastern U.S. Volume II:
Preparation. EPA 600/4-87/030. U.S. Environmental Protection Agency, Environmental
Monitoring Systems Laboratory, Las Vegas, Nevada. 142 pp.
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1.0 Introduction
1.1 Aquatic Effects Research Program Handbooks
Numerous private, state, and federal groups have initiated research projects similar to those
developed as components of the Aquatic Effects Research Program (AERP). Existing AERP field and
laboratory manuals and quality assurance plans were not written for an overall methods application
or for general use. Developed for specific survey requirements, available operational documents do
not provide general guidelines and procedures that can be adapted readily by different research
groups. The AERP handbooks are designed to fill this gap. As guidance documents for groups
involved in acid deposition monitoring activities, the handbooks enable researchers to avoid
duplication of efforts and to make maximum use of tested methods.
/. /. / Types of Handbooks
The AERP handbooks focus on surface water chemistry, based on documents written for the
National Surface Water Survey (NSWS), and on soil chemistry, based on Direct/Delayed Research
Project (DDRP) reports. The handbooks contain procedures for field operations, laboratory
operations, and quality assurance (QA) criteria for water and soil monitoring activities. Surface
water chemistry and soil chemistry are discussed in separate, three-volume sets.
/. 1.2 Structure of Volumes
Because AERP is a dynamic program, each document is contained in a three-ring binder to
facilitate the insertion of additions or modifications. Each document contains an independent Table
of Contents with titles, revision numbers, and effective dates of revisions; a complete, updated Table
of Contents accompanies the dissemination of each revision. The availability of each volume or
revision is announced in the AERP status.
1.1.3 Interrelationship of Volumes
Each volume of a particular handbook set represents one aspect of an acid deposition moni-
toring activity. Collectively, the field, laboratory, and QA handbooks offer a comprehensive guide to
surface water chemistry and soil chemistry monitoring.
1.2 Content of Laboratory Analyses Handbook
This handbook describes methods used to process and analyze soil samples. These
procedures are based on methods used during the three soil surveys comprising the DDRP. Most
of the methods were originally based on methodologies employed by the U.S. Department of
Agriculture/Soil Conservation Service (USDA/SCS), including methods described in the National Soils
Handbook (USDA/SCS, 1983), Soil Survey Manual (USDA/SCS, 1951, supplement 1962), Field Study
Program Elements to Assess the Sensitivity of Soils to Acid Deposition Induced Alterations in Forest
Productivity (Fernandez, 1983), Procedures for Collecting Soil Samples and Methods of Analysis for
Soil Surveys (USDA/SCS), Methods of Soil Analysis, Part /(Klute, 1986) and Part2(Page et al., 1982),
Soil Taxonomy (USDA/SCS, 1975), Keys to Soil Taxonomy (USDA/SCS, 1988), and Soil Survey
Laboratory Methods and Procedures for Collecting Soil Samples (USDA/SCS, 1984). These original
methodologies were extensively modified to meet the particular needs of the DDRP. Modifications
included specifications for sample sizes, QAand quality control (QC) samples, soil-to-solution ratios,
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extraction times, extraction apparatus, holding times, standard internal quality control procedures,
and standard or automated equipment. These methods have been further revised based on the
results of the DDRP soil surveys.
The chemical and physical parameters measured, the parameter codes used in this document,
the analytical methods used, and the section in this document where they are discussed are listed
in Table 1-1.
Table 1-1. Parameter Descriptions and Codes
Section
Parameter(s)
Parameter Code(s)
Description of Parameter
Percent fine gravel
Percent medium gravel
Bulk density-clod
RF FG
RF MG
BD CLD
Bulk density-known vol-
ume
BD KV
Field-moist pH
PH MP
Percent fine gravel is the portion of the bulk
sample with rock fragment diameter be-
tween 2 mm and 4.75 mm determined by
sieving.
Percent medium gravel is the portion of the
bulk sample with rock fragment diameter
between 4.75 mm and 20 mm, determined
by sieving.
Bulk density is the weight of dry soil per
unit volume, including pore space. In the
clod method, the bulk density is derived by
calculation using air-dry and oven-dry
weights of a Saran-coated clod.
Bulk density is the weight of dry soil per
unit volume, including pore space. In the
known volume method, the bulk density is
derived by calculation using air-dry and
oven-dry weights of volume replacement or
volume filling soil sample.
pH of a field-moist sample, determined in a
deionized water extract using a 1:1 mineral
soil to solution ration or 1:5 organic soil to
solution ratio, measured with a pH meter
and combination electrode.
Loss-on-ignition (percent
organic matter)
OM LOI
Loss-on-ignition provides an estimate of
organic matter, determined by calculation
using oven-dry and ashed-weights.
(continued)
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Table 1-1. (Continued)
Section
Parameter(s)
Parameter Code(s)
Description of Parameter
Soil moisture
MOIST
Percent total sand
SAND
Air-dry soil moisture measured and
expressed as a percentage on an oven-dry
weight basis; mineral soils are dried at
105°C, organic soils at 60°C.
Total sand is the portion of the sample
with particle diameter between 0.05 mm
and 2.0 mm, and is calculated as the sum-
mation of percentages for individual sand
fractions: VCOS + COS + MS + FS + VFS.
Percent very coarse sand VCOS
Percent coarse sand
COS
Percent medium sand
MS
Percent fine sand
Percent very fine sand
FS
VFS
Very coarse sand is the sand fraction be-
tween 1.0 mm and 2.0 mm; it is determined
by sieving the sand which has been
separated from the silt and clay.
Coarse sand is the sand fraction between
0.5 mm and 1.0 mm; it is determined by
sieving the sand which has been separated
from the silt and clay.
Medium sand is the sand fraction between
0.25 mm and 0.50 mm; it is determined by
sieving the sand which has been separated
from the silt and clay.
Fine sand is the sand fraction between 0.10
mm and 0.25 mm; it is determined by
sieving the sand which has been separated
from the silt and clay.
Very fine sand is the sand fraction between
0.05 mm and 0.10 mm; it is determined by
sieving the sand which has been separated
from the silt and clay.
(continued)
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Table 1-1. (Continued)
Section
Parameter(s)
Parameter Code(s)
Description of Parameter
Percent total silt
SILT
Total silt is the portion of the sample with
particle diameter between 0.002 mm and
0.05 mm; it is calculated by subtracting
from 100 percent the sum of the total sand
and clay.
Percent coarse silt
COSI
Coarse silt is the silt fraction between 0.02
mm and 0.05 mm; it is calculated by
subtracting the fine silt fraction from the
total silt.
Percent fine silt
FSI
Fine silt is the silt fraction between 0.002
mm and 0.02 mm; it is determined by pipet-
ting and is calculated by subtracting the
clay fraction from the less than 0.02-mm
fraction.
10
Percent total clay CLAY
pH in deionized water PHJH20
Total clay is the portion of the sample with
particle diameter of less than 0.002 mm; it
is determined by pipetting.
pH is determined in a deionized water
extract using a 1:1 mineral soil to solution
ratio or 1:5 organic soil to solution ratio; it
is measured with a pH meter and combina-
tion electrode.
10
pH in 0.002 M calcium
chloride
PH 002M
pH is determined in a 0.002 M calcium chlo-
ride extract using a 1:2 mineral soil to
solution ratio or 1:10 organic soil to solution
ratio; it is measured with a pH meter and
combination electrode.
10
pH in 0.01 M calcium
chloride
PH 01M
pH is determined in a 0.01 M calcium
chloride extract using a 1:1 mineral soil to
solution ratio or 1:5 organic soil to solution
ratio; it is measured with a pH meter and
combination electrode.
(continued)
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Table 1-1. (Continued)
Section
Parameter(s)
Parameter Code(s)
Description of Parameter
11
11
12
Cation exchange
capacity (ammonium
chloride saturating
solution)
CEC CL
Cation exchange
capacity (ammonium
acetate saturating
solution)
CEC OAC
Calcium exchangeable in
ammonium acetate
CA OAC
Cation exchange capacity, determined with
an unbuffered 1 M ammonium chloride
solution is the effective CEC which occurs
at approximately the field pH when com-
bined with the acidity component; approxi-
mately 1:13 mineral soil to solution ratio or
1:52 organic soil to solution ratio are used;
samples are analyzed for ammonium con-
tent by one of three methods: automated
distillation/titration, manual distilla-
tion/automated titration, or ammonium
displacement/flow injection analysis.
Cation exchange capacity determined with
1 M ammonium acetate solution buffered at
pH 7.0 is the theoretical estimate of the
maximum potential CEC for a specific soil
when combined with the acidity compo-
nent; approximately 1:13 mineral soil to
solution ratio or 1:52 organic soil to solution
ratio are used; samples are analyzed for
ammonium content by one of three meth-
ods: automated distillation/titration,
manual distillation/automated titration, or
ammonium displacement/flow injection
analysis.
Exchangeable calcium determined with 1 M
ammonium acetate solution buffered at pH
7.0; approximately 1:13 mineral soil to
solution ratio or 1:52 organic soil to solution
ratio are used; atomic absorption spec-
trometry or inductively coupled plasma
atomic emission spectrometry is specified.
(continued)
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Table 1-1. (Continued)
Section
Parameter(s)
Parameter Code(s)
Description of Parameter
12
Magnesium, exchange-
able in ammonium ace-
tate
MG OAC
12
Potassium, exchangeable
in ammonium acetate
K OAC
12
Sodium, exchangeable in
ammonium acetate
NA OAC
13
Calcium, exchangeable in
ammonium chloride
CA CL
13
Magnesium, exchange-
able in ammonium chlo-
ride
MG CL
Exchangeable magnesium is determined
with 1 M ammonium acetate solution
buffered at pH 7.0; approximately 1:13
mineral soil to solution ratio or 1:52 organic
soil to solution ratio are used; atomic
absorption spectrometry or inductively
coupled plasma atomic emission spectrom-
etry is specified.
Exchangeable potassium is determined
with 1 M ammonium acetate solution
buffered at pH 7.0; approximately 1:13
mineral soil to solution ratio or 1:52 organic
soil to solution ratio are used; atomic
absorption spectrometry or emission
spectroscopy is specified.
Exchangeable sodium is determined with 1
M ammonium acetate solution buffered at
pH 7.0; approximately 1:13 mineral soil to
solution ratio or 1:52 organic soil to solution
ratio are used; atomic absorption spec-
trometry, inductively coupled plasma atomic
emission spectrometry, or emission spec-
trometry is specified.
Exchangeable calcium is determined with
an unbuffered 1 M ammonium chloride solu-
tion; approximately 1:13 mineral soil to
solution ratio or 1:52 organic soil to solution
ratio are used; atomic absorption
spectrometry or inductively coupled plasma
atomic emission spectrometry is specified.
Exchangeable magnesium is determined
with an unbuffered 1 M ammonium chloride
solution; approximately 1:13 mineral soil to
solution ratio or 1:52 organic soil to solution
ratio are used; atomic absorption spec-
trometry or inductively coupled plasma
atomic emission spectrometry is specified.
(continued)
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Table 1-1. (Continued)
Section
Parameter(s)
Parameter Code(s)
Description of Parameter
13
Potassium, exchangeable
in ammonium chloride
K CL
Exchangeable potassium is determined
with an unbuffered 1 M ammonium chloride
solution; approximately 1:13 mineral soil to
solution ratio or 1:52 organic soil to solution
ratio are used; atomic absorption spec-
trometry or emission spectroscopy is speci-
fied.
13
Sodium, exchangeable in
ammonium chloride
NA CL
13
Aluminum, exchangeable
in ammonium chloride
AL CL
14
Calcium, exchangeable in
calcium chloride
CA CL2
14
Magnesium, exchange-
able in calcium chloride
MG CL2
Exchangeable sodium is determined with
an unbuffered 1 M ammonium chloride solu-
tion; approximately 1:13 mineral soil to
solution ratio or 1:52 organic soil to solution
ratio are used; atomic absorption
spectrometry, inductively coupled plasma
atomic emission spectrometry, or emission
spectroscopy is specified.
Exchangeable aluminum is determined with
an unbuffered 1 M ammonium chloride
solution; approximately 1:13 mineral soil to
solution ratio or 1:52 organic soil to solution
ratio are used; inductively coupled plasma
atomic emission spectrometry is specified.
Extractable calcium is determined by a
0.002 M calcium chloride extraction; a 1:2
mineral soil to solution ratio or 1:10 organic
soil to solution ratio are used; the calcium
is used to calculate lime potential; atomic
absorption spectrometry or inductively
coupled plasma atomic emission spectrom-
etry is specified.
Extractable magnesium is determined by a
0.002 M calcium chloride extraction; a 1:2
mineral soil to solution ratio or 1:10 organic
soil to solution ratio are used; atomic
absorption spectrometry or inductively
coupled plasma atomic emission spectrom-
etry is specified.
(continued)
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Table 1-1. (Continued)
Section
Parameter(s)
Parameter Code(s)
Description of Parameter
14
Potassium, exchangeable
in calcium chloride
K CL2
Extractable potassium is determined by a
0.002 M calcium chloride extraction; a 1:2
mineral soil to solution ratio or 1:10 organic
soil to solution ratio are used; atomic
absorption spectrometry or emission spec-
trometry is specified.
14
Sodium, exchangeable in
calcium chloride
NA CL2
14
Iron, exchangeable in
calcium chloride
FE CL2
14
Aluminum, exchangeable
in calcium chloride
AL CL2
15
16
Exchangeable acidity in
barium chloride
Iron, extractable in pyro-
phosphate
AC BACL
FE PYP
Extractable sodium is determined by a
0.002 M calcium chloride extraction; a 1:2
mineral soil to solution ratio or 1:10 organic
soil to solution ratio are used; atomic
absorption spectrometry, inductively
coupled plasma atomic emission spectrom-
etry, or emission spectroscopy is specified.
Extractable iron is determined by a 0.002 M
calcium chloride extraction; a 1:2 mineral
soil to solution ratio or 1:10 organic soil to
solution ratio are used; inductively coupled
plasma atomic emission spectrometry is
specified.
Extractable aluminum is determined by a
0.002 M calcium chloride extraction; a 1:2
mineral soil to solution ratio or 1:10 organic
soil to solution ratio are used; the alumi-
num concentration obtained from this
procedure is used to calculate aluminum
potential; inductively coupled plasma atom-
ic emission spectrometry is specified.
Total exchangeable acidity is determined by
titration in a buffered (pH 8.2) barium
chloride triethanolamine extraction using an
approximately 1:30 soil to solution ratio.
Extractable iron is determined by a 0.1 M
sodium pyrophosphate extraction using a
1:100 soil to solution ratio; the pyrophos-
phate extract estimates organically-bound
iron; inductively coupled plasma atomic
emission spectrometry is specified.
(continued)
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Table 1-1. (Continued)
Section
Parametec(s)
Parameter Code(s)
Description of Parameter
16
16
16
16
16
16
Aluminum, extractable in
pyrophosphate
AL PYP
Iron, extractable in acid-
oxalate
FE AO
Aluminum, extractable in
acid-oxalate
AL AO
Silicon, extractable in
acid-oxalate
SI AO
Iron, extractable in
citrate-dithionite
FE CD
Aluminum, extractable in
citrate-dithionite
AL CD
Extractable aluminum is determined by a
0.1 M sodium pyrophosphate extraction
using a 1:100 soil to solution ratio; the
pyrophosphate extract estimates organical-
ly-bound aluminum; inductively coupled
plasma atomic emission spectrometry is
specified.
Extractable iron is determined by an
ammonium oxalate-oxalic acid extraction
using a 1:100 soil to solution ratio; the acid
oxalate extract estimates organic and
amorphous iron oxides; inductively coupled
plasma atomic emission spectrometry is
specified.
Extractable aluminum is determined by an
ammonium oxalate-oxalic acid extraction
using a 1:100 soil to solution ratio; the acid
oxalate extract estimates organic and
amorphous aluminum oxides; inductively
coupled plasma atomic emission spectrom-
etry is specified.
Extractable silicon is determined by an am-
monium oxalate-oxalic acid extraction using
a 1:100 soil to solution ratio; inductively
coupled plasma atomic emission spectrom-
etry is specified.
Extractable iron is determined by a sodium
citrate-sodium dithionite extraction using a
1:30 soil to solution ratio; the citrate
dithionite extract estimates non-silicate
iron; inductively coupled plasma atomic
emission spectrometry is specified.
Extractable aluminum is determined by a
sodium citrate-sodium dithionite extraction
using a 1:30 soil to solution ratio; the
citrate dithionite extract estimates non-
silicate aluminum; inductively coupled
plasma atomic emission spectrometry is
specified.
(continued)
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Table 1-1. (Continued)
Section
Parameter(s)
Parameter Code(s)
Description of Parameter
17
Sulfate, extractable in
deionized water
SO4 H2O
17
Sulfate, extractable in
sodium phosphate
SO4 PO4
18
Sulfate, 0 mg S/L
isotherm
S04 0
18
Sulfate, 2 mg S/L
isotherm
SO4 2
18
Sulfate, 4 mg S/L
isotherm
SO4 4
Extractable sulfate is determined with a
double deionized water extract; this extrac-
tion approximates the sulfate which will
readily enter the soil solution and uses a
1:20 mineral soil to solution ratio or 1:40
organic soil to solution ratio; ion chroma-
tography is specified.
Extractable sulfate is determined with a
0.016 M sodium phosphate (500 mg P/L)
extract; this extraction approximates the
total amount of adsorbed sulfate and uses
a 1:20 mineral soil to solution ratio or 1:40
organic soil to solution ratio; ion chroma-
tography is specified.
Sulfate remaining in a 0 mg S/L solution
following equilibration with a 1:5 mineral
soil to solution ratio or 1:20 organic soil to
solution ratio; the data are used to develop
sulfate isotherms; ion chromatography is
specified.
Sulfate remaining in a 2 mg S/L solution
following equilibration with a 1:5 mineral
soil to solution ratio or 1:20 organic soil to
solution ratio; the data are used to develop
sulfate isotherms; ion chromatography is
specified.
Sulfate remaining in a 4 mg S/L solution
following equilibration with a 1:5 mineral
soil to solution ratio or 1:20 organic soil to
solution ratio; the data are used to develop
sulfate isotherms; ion chromatography is
specified.
(continued)
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Table 1-1. (Continued)
Section
Parameter(s)
Parameter Code(s)
Description of Parameter
18
Sulfate, 8 mg S/L
isotherm
SO4 8
18
Sulfate, 16 mg S/L
isotherm
SO4 16
18
Sulfate, 32 mg S/L
isotherm
SO4 32
19
Total carbon
C TOT
19
Total nitrogen
N TOT
Sulfate remaining in a 8 mg S/L solution
following equilibration with a 1:5 mineral
soil to solution ratio or 1:20 organic soil to
solution ratio; the data are used to develop
sulfate isotherms; ion chromatography is
specified.
Sulfate remaining in a 16 mg S/L solution
following equilibration with a 1:5 mineral
soil to solution ratio or 1:20 organic soil to
solution ratio; the data are used to develop
sulfate isotherms; ion chromatography is
specified.
Sulfate remaining in a 32 mg S/L solution
following equilibration with a 1:5 mineral
soil to solution ratio or 1:20 organic soil to
solution ratio; the data are used to develop
sulfate isotherms; ion chromatography is
specified.
Total carbon is determined by rapid oxida-
tion followed by infrared detection or
thermal conductivity detection using an
automated CHN analyzer; total carbon can
be used to characterize the soil organic
matter.
Total nitrogen is determined by rapid oxida-
tion followed by infrared detection or ther-
mal conductivity detection using an auto-
mated CHN analyzer; total nitrogen can be
used to characterize the soil organic mat-
ter.
20
Total sulfur
S TOT
Total sulfur is determined by automated
sample combustion followed by infrared
detection of evolved sulfur dioxide.
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1.3 Overview of the DDRP
Concern about the effects of acidic deposition on the Nation's surface water resources led
the U.S. Environmental Protection Agency (EPA) to initiate research in the field in the late 1970s.
Early research, focusing on a diversity of potential effects, provided insight into those research
areas which were considered central to key policy questions. Recognizing the need for an
integrated, stepwise approach to resolve the issues, EPA implemented the AERP in 1983 with its
present structure, focus, and approach. The AERP is also a major component of the National Acid
Precipitation Assessment Program's (NAPAP) Aquatic Effects Research Task Group 6, a cooperative
effort of nine federal agencies tasked with addressing important policy and assessment questions
relating to the acidic deposition phenomenon and its effects.
The DDRP is one of the major component projects within the AERP. Its principal mandate is
to make regional projections of future effects of sulfur deposition on long-term surface water
chemistry based on the best available data and most widely accepted hypotheses of the
acidification process (Church et al., 1989). Regional survey boundaries for DDRP component projects
are based on Land Resource Regions and Major Land Resource Areas of the Northeast United
States. (USDA/SCS, 1985). Specific objectives of the DDRP are:
• To describe the regional variability of soil and watershed characteristics.
• To determine which soil and watershed characteristics are most strongly related to surface
water chemistry.
• To estimate the relative importance of key watershed processes in moderating regional
effects of acidic deposition.
• To classify a sample of watersheds with regard to their response characteristics to inputs
of acidic deposition and to extrapolate the results from this sample of watersheds to the
study regions.
Watershed retention of atmospherically deposited sulfur is an important consideration within
the DDRP, as are the dynamics of retention via soil sulfate adsorption. Also considered are "single-
factor" models (Bloom and Grigal, 1985; Reuss and Johnson 1985, 1986) of the influence of acidic
deposition on the supply of base cations from soils to surface waters. The purpose of this
modeling is to evaluate the potential relative importance of cation exchange as a process mediating
surface water acidification. (Church et al., 1989.)
Watershed models are used in the DDRP to project future, integrated effects of atmospheric
sulfur deposition on surface water chemistry. Three models specifically developed to investigate
the effects of acidic deposition on watersheds and surface waters are used: (1) the Model of
Acidification of Groundwater in Catchments (MAGIC) (Cosby et al., 1985a,b; 1986a,b), (2) the
Enhanced Trickle Down (ETD) Model (Lee. 1987; Nikolaidis et al., 1988; Schnoor et al., 1986); and (3)
the Integrated Lake-Watershed Acidification Study (ILWAS) Model (Chen et al., 1983; Gherini et al.,
1985). The three models are run using common data sets for forcing functions (e.g., rainfall, runoff,
atmospheric deposition) and data aggregated from the DDRP soils data base for state variables
(e.g., soil physical and chemical variables). Projections of changes in annual average surface water
chemistry are being made for each region for at least 50 years for two scenarios of atmospheric
sulfur deposition (Church et al., 1989).
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1.4 References
Bloom, P. R., and D. F. Grigal. 1985. Modeling soil response to acidic deposition in non-sulfate
adsorbing soils. J. Environ, dual. 14:489-495.
Chen, C. W., S. A Gherini, J. D. Dean, R. J. M. Hudson, and R. A. Goldstein. 1983. Modeling of
Precipitation Series, Volume 9. Ann Arbor Sciences, Butterworth Publishers, Boston, MA,
Church, M. R., K. W. Thorton, P. W. Shaffer, D. L Stevens, B. P. Rochelle, G. R. Holdren, M. G.
Johnson, J. J. Lee, R. S. Turner, D. L. Cassell, D. A. Lammers, W. G. Campbell, C. I. Liff,
C. C. Brandt, L. H. Liegel, G. D. Bishop, D. C. Mortenson, S. M. Pierson and D. D. Schmoyer.
1989. Future Effects of Long- Term Sulfur Deposition on Surface Water Chemistry in the
Northeast and Southern Blue Ridge Province: Results of the Direct/Delayed Response Project.
U.S. Environmental Protection Agency, EPA/600/3-89/061, Washington, D.C.
Cosby, B. J., G. M. Hornberger, J. N. Galloway, and R. F. Wright. 1985a. Modeling the effects of
acid deposition: Assessment of a lumped parameter model of soil water and streamwater
chemistry. Water Resour. Res. 21:51-63.
Cosby, B. J., G. M. Hornberger, J. N. Galloway, and R. F. Wright. 1985b. Time scales of catchment
acidification: A quantitative model for estimating freshwater acidification. Environ. Sci.
Techno!. 19:1144-1149.
Cosby, B. J., G. M. Hornberger, E. B. Rastetter, J. N. Galloway, and R. F. Wright. 1986a. Estimating
catchment water quality response to acid deposition using mathematical models of soil ion
exchange processes. Geoderma 38:77-95.
Cosby, B. J., G. M. Hornberger, R. F. Wright, and J. N. Galloway. 1986b. Modeling the effects of
acid deposition: control of long-term sulfate dynamics by soil sulfate adsorption. Water
Resour. Res. 22:1283-1292.
Fernandez, I. 1983. Field Study Program Elements to Assess the Sensitivity of Soils to Acidic
Deposition Induced Alterations in Forest Productivity. National Council of the Paper Industry
for Air and Stream Improvement, Inc. (NCASI) Technical Bulletin, No. 404.
Gherini, S. A., L. Mok, R. J. Hudson, G. F. Davis, C. W. Chen, and R. A Goldstein. 1985. The ILWAS
model: Formulation and application. Water, Air, Soil Pollut. 26:425-459.
Klute, A, (ed). 1986. Methods of Soil Analysis: Part 1. Physical and Mineralogical Methods.
Agronomy Monograph No. 9, 2nd edition. American Society of Agronomy/Soil Science Society
of America, Madison, Wisconsin.
Lee, S. 1987. Uncertainty Analysis for Long-term Acidification of Lakes in Northeastern USA Ph.D.
Thesis. University of Iowa, Iowa City.
Nikolaidis, N. P., H. Rajaram, J. L. Schnoor, and K. P. Georgakakos. 1988. A generalized soft water
acidification model. Water Resour. Res. 24:1983-1996.
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Page, A. L, R. H. Miller, and D. R. Keeney (eds.). 1982. Methods of Soil Analysis: Part 2, Chemical
and Microbiological Properties. Agronomy Monograph No. 9, 2nd Edition. American Society of
Agronomy/Soil Science Society of America, Madison, Wisconsin.
Reuss, J. O., and D. W. Johnson. 1985. Effect of soil processes on the acidification of water by
acid deposition. J. Environ. Oual. 14:26-31.
Reuss, J. O., and D. W. Johnson. 1986. Acid Deposition and the Acidification of Soils and Waters.
Ecological Studies Volume 59. Springer-Verlag, Inc., New York, New York.
Schnoor, J. L., N. P. Nikolaidis, and G. E. Glass. 1986. Lake resources at risk to acidic deposition
in the Upper Midwest. J. Water Pollut. Control Fed. 58:139-148.
U.S. Department of Agriculture/Soil Conservation Service. 1951. Supplement 1962. Soil Survey Manu-
al. Agriculture Handbook No. 18, U.S. Department of Agriculture, Washington, D.C.
U.S. Department of Agriculture/Soil Conservation Service. 1972. Procedures lor Collecting Soil
Samples and Methods of Analysis for Soil Surveys. Soil Survey Investigations Report No. 1,
U.S. Department of Agriculture. U.S. Government Printing Office, Washington, D.C.
U.S. Department of Agriculture/Soil Conservation Service. 1975. Soil Taxonomy: A Basic System
of Soil Classification for Making and Interpreting Soil Survey. Agriculture Handbook No. 436,
U.S. Department of Agriculture, U.S. Government Printing Office, Washington, D.C.
U.S. Department of Agriculture/Soil Conservation Service. 1983a. National Soils Handbook. Title
430, U.S. Department of Agriculture, Washington, D.C.
U.S. Department of Agriculture/Soil Conservation Service. 1984. Soil Survey Laboratory Methods and
Procedures for Collecting Soil Samples. Soil Survey Investigations Report No. 1, USDA. U.S.
Government Printing Office, Washington, D.C.
U.S. Department of Agriculture/Soil Conservation Service. 1985. Land Resource Regions and Major
Land Resource Areas of. the Northeast United States (map). U.S. Department of Agriculture,
Fort Worth, Texas.
U.S. Department of Agriculture/Soil Conservation Service. 1988. Keys to Soil Taxonomy. Technical
Monograph No. 6, U.S. Department of Agriculture/Agronomy Department, Cornell University,
Ithaca, New York.
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2.0 Preparation Laboratory Facilities and Organization
Large regional surveys, such as those conducted in the DDRP, result in the collection of
numerous samples. Analysis should be efficient and prompt to permit resampling to be conducted,
if necessary to replace lost or destroyed samples. Such surveys may require the use of multiple
analytical laboratories. In such cases, a preparation laboratory may be a desirable option.
The preparation laboratory is designed to be the link between the sampling crews and the
analytical laboratories. The primary functions of the preparation laboratory are to prepare
homogeneous subsamples from processed bulk samples and to transfer batches of those
subsamples to the analytical laboratories. For these tasks to be successfully accomplished, the
preparation laboratory must uniformly track, process, and store all samples.
The preparation laboratory staff may also perform certain soil analyses. These include the
determinations of percent air-dry moisture, percent rock fragments in the 2- to 20-mm fractions,
percent organic matter content by loss-on-ignition, field-moist pH in water, and bulk density.
2.1 Facilities Requirements
The soil preparation and preliminary analyses should be performed in a secure, dust-free,
climate-controlled area. Fume hoods and exhaust fans must be operable for certain stages of
sample processing and for the preparation of the Saran:acetone solution. A source of filtered,
compressed air must be available for routine cleaning of equipment. Oeionized water is required
in the preparation laboratory for various analyses and cleaning. Cold storage facilities must be
readily accessible with ample space to store bulk samples. Additionally, the hardware and supplies
listed in Table 2-1 are required for the soil processing and analysis procedures.
Table 2-1. Preparation Laboratory Supplies
•Log books
•Raw data forms
•Munsell color book
• Pens, indelible black ink
•Kraft paper, 36" wide rolls
•Plastic gloves (unpowdered)
•Dust masks
•One-gallon paint cans
•Aluminum weighing tins
•Nalgene bottles: 2-L, 500-mL, 125-mL
• Carboys, 13-gallon capacity
•Crucibles, tolerance to 450 *C
•Evaporating dishes, tolerance to 450 'C
• Beakers, 1000-mL
•Tongs
•Ring stand
• Thermometers, 0 to 100 *C range
•Sample drying tables, PVC / nylon mesh
•Rolling pins, wooden
• Rubber stoppers, No. 10 size
•Brass sieves, square-holed: 2-mm and 4.75-mm
•Riffle splitter, Jones-type, closed-bin, with 1.25-cm baffles
•Analytical balance, accurate to 0.01 g, capacity to 500 g
•Open-pan balance, accurate to 0.1 g, capacity to 5 kg
•Balance calibration weights, 3 to 5 weights bracketing
expected range
•pH meter, with proper electrodes
•Desiccators
• Desiccant
•Hot plate
•Convection oven
•Muffle furnace
•Shipping boxes
•Packing material
•Strapping tape
•Saran powder
•Acetone
•Plastic containers: 25-mL, 50-mL
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2.2 Staffing
The preparation laboratory staff consists of a laboratory manager and a number of analysts.
The preparation laboratory manager should be knowledgeable of laboratory methods and procedures
and should have supervisory skills. Adequate staffing should be provided to ensure a fast and
efficient turnaround of samples from the field to the analytical laboratories. All personnel should
be thoroughly trained to perform the protocols and procedures before the sample processing begins.
Sampling crews ship samples to the preparation laboratory by using an overnight express
service. The preparation laboratory manager assumes the responsibility for maintaining the integrity
of all samples at the laboratory facility. After the samples have been processed and analyzed, they
are assembled in batches and shipped to designated analytical laboratories for further analyses.
An important function of batch formation is to place certain quality evaluation (QE) and quality
control (QC) samples in the batches without revealing their identity to the analytical laboratories.
A separate function of the preparation laboratory is to distribute equipment and supplies to the
sampling crews. The preparation laboratory should maintain thorough documentation of sample
tracking and processing. All documentation should be available to and reviewed by quality
assurance (QA) personnel during the course of the survey.
Ultimately, the laboratory manager is responsible for assigning duties according to the specific
project needs. The following division of responsibilities is presented as an example.
Laboratory Manager:
Coordinates laboratory operations and time management.
Communicates with the QA manager and staff.
Communicates with project management personnel.
Oversees sample receipt and storage.
Oversees all computer data entry and evaluation procedures.
Oversees sample preparation and analysis activities.
Organizes analytical samples into batches.
Tracks all samples during processing.
Laboratory Analysts:
Enter data into computer entry and verification system.
Run verification programs.
Receive and log samples at cold storage.
Organize cold storage space.
Track all samples during processing.
Spread samples to air dry.
Perform field-moist pH determinations.
Perform loss-on-ignition determinations.
Perform air-dry moisture determinations.
Disaggregate and sieve bulk samples.
Perform rock fragment determinations.
Homogenize bulk samples with riffle splitter.
Create appropriate analytical and archive subsamples.
Perform bulk density determinations.
Complete necessary information on bulk sample processing sheet.
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Additional Laboratory Analysts (part-time):
• Disaggregate and sieve bulk samples.
• Perform rock fragment determinations.
• Track all equipment (both field and laboratory).
• Coordinate equipment procurement, preparation, and distribution.
2.3 Training
Recommended qualifications for preparation laboratory personnel include a knowledge of basic
chemistry, laboratory experience, and a high level of work quality and precision. A college degree
in one of the physical sciences is recommended, but is not absolutely necessary. The nature of
preparation laboratory work demands close attention to detail and the ability to perform at a
consistently high level of quality.
Laboratory training programs should include complete coverage of each procedure and hands-
on practice sessions. The theory and rationale for each laboratory rule and procedure should be
covered in detail. A written laboratory manual that contains detailed, step-by-step procedures is
invaluable during training. A typical training schedule should include one day of orientation (including
an explanation of laboratory rules and an overview of operations). Another day should be devoted
to explaining each method or procedure, including general laboratory procedures (Appendix A). This
training should include a lecture, an observation period, a question and answer period, and hands-on
practice. At the conclusion of training, written testing is recommended with follow-up, supervised
practice in any areas of weakness. Each analyst should be fully trained in all areas to provide
coverage for absences and potential for rotation of duties.
Particular emphasis should be placed on avoiding sample contamination throughout training
and operation. Disposable sterile gloves and lab coats should be worn when handling samples.
As much as possible, all sample handling should be done inside the clean air station. Eating and
smoking are forbidden inside the laboratory and all personnel should wash their hands after breaks.
Personnel should not wear makeup or perfume, including men's cologne. All glassware and plastic
ware should be washed in deionized water meeting American Society of Testing and Materials
(ASTM) specifications for Type I reagent grade water (ASTM, 1984). When adding reagents to
samples, the pipet tip should not contact the sample. Acid-washed and deionized water-washed
apparatus and glassware should be stored separately and both types should be labeled clearly.
Counter areas should be covered in Benchkote or kraft paper which should be changed frequently.
The laboratory floors and counters should be washed and swept daily. Only water should be used
for washing; no soap should be used. Additional precautions regarding contamination avoidance
are described in the methods relating to sample processing.
2.4 Safety
Safety is also a primary consideration in the laboratory. In most locales, inspection and
certification by the local fire department is required. Smoke detectors and class A-B fire
extinguishers are recommended and may be required.
Fire escape routes should be clearly marked and each person should be aware of least two
escape routes from the work area. A circuit breaker with a main switch shutoff should be easily
accessible to avert electrical problems. Chemicals should be stored in approved containers and
cabinets; bases and acids should be stored in separate areas. Chemical spill kits should be located
in each work area. Disaster plans should be developed and included in training so that each person
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knows exactly what to do in the event of an accident. Copies of disaster plans should also be
provided to the local fire department or emergency rescue team and may be required by local
ordinance. Emergency numbers should be posted next to each telephone.
Personnel safety includes wearing proper laboratory clothing (e.g., laboratory coat, fitted safety
glasses or goggles, and protective footwear). If hazardous substances are used, personnel should
be fitted for half-mask respirators with organic cartridges. Personnel should be certified in cardio-
pulmonary resuscitation (CPR) and first aid; local Red Cross or American Heart Association groups
can provide classes for a nominal fee. A medical surveillance program, including testing before and
after sample handling, is recommended if hazardous materials are used. A complete physical,
including blood testing, is recommended prior to initiation of potentially hazardous laboratory
activities.
2.5 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01.
Standard Specifications for Reagent Water, D 1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
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3.0 General Laboratory Procedures
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This section outlines general laboratory procedures used by the preparation and analytical
laboratories. The detailed procedures for analyzing physical and chemical parameters are described
in sections 4.0 through 20.0.
3.1 Sample Handling
3.1.1 Preparation Laboratory Sample Receipt and Tracking
In the DDRP, four types of soil samples are sent to the preparation laboratory. These are:
(1) bulk samples (routine and duplicate), (2) field audit samples, (3) clod bulk density samples, and
(4) known volume bulk density samples. Field sampling procedures are described in the field
sampling manuals for the DDRP (Blume et at., 1987a, and Blume et al., 1987b); and will be detailed
in the Handbook of Methods for Acid Deposition Studies, Field Methods lor Soil Chemistry.
Bulk samples are those soil samples taken from a designated portion of a specific horizon.
A bulk sample contains approximately one gallon of soil and generally weighs about 5.5 Kg. The
bulk samples are deposited in large plastic bags and placed within protective outer canvas bags.
Each bulk sample should arrive at the laboratory with a completed DDRP Label A (Figure 3-1) affixed
to the inner plastic bag.
Field audit samples are quality evaluation (QE) samples sent by QA staff to the sampling
crews for inclusion in the sampling of every third pedon by each crew. The samples are sieved,
packaged, and shipped in the same manner as their associated routine samples. Each field audit
sample should arrive at the laboratory with a completed DDRP Label A affixed to the inner plastic
bag. Both mineral and organic horizons are sampled; for the DDRP, organic soils are defined as
having 20 percent or more organic matter as determined by loss-on-ignition.
Clod samples are fist-sized, structurally intact, bulk density samples taken from designated
horizons. Each clod is wrapped in a hairnet and dipped briefly in a 1:5 Saran:acetone solution to
help maintain the clod structure and reduce moisture loss from the clod during transport and
storage. Each clod is labeled, covered by a small plastic bag, and placed in a special clod box with
dividers.
NADSS Label A
Date Sampled:
D D MMMY Y
Crew ID:
Site ID:
Sample Code:
Horizon: Depth:_
Set ID:
cm
Figure 3-1. DDRP Label A.
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Known volume bulk density samples are taken from horizons where clods are unobtainable.
Two types of known volume samples, volume replacement (VR) and volume filling (VF) samples, are
used in the DORP. These bulk density samples are packaged in small, pre-labeled plastic bags in
much the same manner as the bulk soil samples.
The sampling crews should make every effort to inform the preparation laboratory when
samples are being shipped from the field. Bulk soil samples, bulk density samples, and field audit
samples are placed in box-enclosed styrofoam coolers with two frozen gel-pacs. The corresponding
field data forms (Appendix B, Figure B-1) and sample shipment forms are sealed in a plastic bag
and taped to the underside of the cooler cover. The outer box of the cooler should be firmly
enclosed with strapping tape. The samples are shipped directly to the preparation laboratory via
overnight carrier.
Because of their fragile nature, the soil clods (one type of bulk density sample) are packed
securely with vermiculite in coolers separate from the bulk soil samples. Clods are stored in a well
ventilated area while awaiting shipment. When samples are shipped, the sampling crew should
notify the preparation laboratory manager to ensure that personnel are available to receive the
samples.
All preparation laboratory personnel should be familiar with the DDRP Label A, as it is a
primary tool used in sample receipt and tracking. Entries on the sample label include the date
sampled, horizon designation, depth range of the horizon sampled, crew identification (ID), site ID,
sample code, and set ID. The crew ID consists of four alpha-numeric characters representing the
state and the crew number assigned to each sampling crew within the state. The site ID is an
assigned code which designates a specific watershed. The set ID is a five-digit code relating to
each day a sampling crew samples a pedon. A range of set IDs is assigned to each crew. The
laboratory personnel also should be familiar with the DDRP Label B (see Figure 3-2) used to label
and track analytical samples within the batches.
The field data form (Appendix B, Figure B-1) is completed by the sampling crew at the
sampling site. The form lists all field data for a particular pedon, including descriptions of landform,
vegetation, soil climate, and a detailed pedon characterization. The field data form also contains
codes (e.g., watershed ID, assigned by the soil sampling task leader).
An adequate tracking system must be initiated to document the transfer of all samples from
the field to the preparation laboratory and, finally, to the analytical laboratory. The following
describes the procedure used to track samples during DDRP:
Before sampling begins, the soil sampling task leader provides the QA manager and
preparation laboratory manager with a list of watershed identification numbers (site IDs) and
pedon numbers for each pedon to be sampled. This information is entered into the computer
entry and verification system at the preparation laboratory prior to sample receipt.
The samples received at the laboratory are checked for coding accuracy against the field data
form and sample shipment form. A sample receipt raw data form (see Appendix B, Figure B-2)
must be filled out completely for all samples received and logged-in at cold storage. This
information is then entered and verified in the computer entry and verification system. The
information is checked against the site IDs and pedon numbers that have been entered into
the program. If a particular watershed/pedon combination has previously been used (e.g., the
preparation laboratory has previously received samples with that watershed/pedon number or
a particular watershed/pedon number cannot be found on the ID list) the soil sampling task
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NADSS
Batch ID
Sample
Label B
No:_
Figure 3-2. DDRP Label B.
leader and the QA manager are to be notified immediately. Samples should not undergo
processing until they are verified under this procedure.
All samples are to be placed in cold storage as soon as possible after receipt. Known volume
bulk density samples, once checked through the sample receipt procedure, can be placed in
the drying area and allowed to air dry. Bulk soil samples and field audit samples remain in
cold storage until there is sufficient space in the drying area for the samples (grouped
according to set ID) to be air dried. After air drying, the samples are returned to cold storage
and must remain there when not being processed.
The cold storage room must be maintained at a temperature of 4 "C. It is necessary for the
temperature to be monitored either by a continuous sensor or by daily thermometer readings.
Any substantial deviations in temperature (± 2 *C or more) should be recorded in a log book;
affected samples should be identified according to set ID and sample code.
Samples should be organized in cold storage so that a particular sample within a given set
may be easily located. Samples arrive at the laboratory in sets which must be maintained
during storage, processing, and shipping. Because organic and mineral analytical samples
are to be batched and shipped separately, it is advisable to keep organic samples separated
from mineral samples in the cold storage area.
3.1.2 Analytical Laboratory Sample Receipt and Tracking
All samples received by the analytical laboratory should be checked in by a receiving clerk who:
(1) records on the shipping form the date samples are received, (2) checks the samples to identify
discrepancies with entries on the shipping form, and (3) mails copies of the completed shipping
form to the appropriate addresses. If there are any discrepancies, or problems such as leakage
or insufficient sample, the discrepancy should be documented and the laboratory or QA manager
should be notified. The receiving clerk should retain a copy of the completed shipping form for the
laboratory records. The samples are refrigerated at 4 *C until sample homogenization can be
performed. Sample homogenization procedures are described in Section 4.6.3.
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After the sample has been homogenized, minimal bottle movement (transport, shaking, etc.)
is warranted to eliminate possible sample resegregation by particle size and density. Bottles must
remain closed (capped) at all times except during aliquot removal for each analysis. Bottles may
remain at room temperature while analyses are being performed. Removal of an aliquot for a given
analysis should be done by a random insertion of a sampler (spatula, scoop, etc.) into the bottle.
NOTE: If bottle will not be used for aliquot extraction for more than 7 days, storage of the
sample at 4 *C is required. Re-warm the sample to room temperature with the bottle
closed (capped) prior to further analysis.
After all analyses have been completed and the results have been checked, the analytical
samples are stored at 4 *C in the event that reanalysis is necessary.
3.2 Quality Control
Quality control (QC) is an integral part of any measurement procedure to ensure that results
are reliable. A summary of internal QC procedures for each method is given in Table 3-1, and copies
of all QC forms are provided in Appendix B. Details on internal QC procedures used in the DDRP
are described below.
3.2.1 Instrument Detection Limits
The instrument detection limits (IDLs) must meet contract-required detection limits (CRDLs);
the CRDLs used in the DDRP are listed in Table 3-2. The IDL is defined as three times the standard
deviation of at least 15 nonconsecutive replicate calibration blank analyses run on a minimum of
three separate days. In some analyses, such as ion chromatography, a signal may or may not be
obtained for a blank analysis. If a signal is not obtained for a blank analysis, the IDL is defined
as three times the standard deviation of 15 nonconsecutive replicate analyses of a standard
(preferably the detection limit quality control check sample (DL-QCCS), see Section 3.2.5) with a
concentration four times the actual detection limit or the CRDL, whichever is less.
3.2.2 Calibration and Standardization
Prepare all calibration standards in concentration units which bracket the expected sample
concentration range without exceeding the linear range of the instrument. Establish a calibration
curve for each analytical method by using a minimum of three points within the linear range. The
use of at least a three-point calibration curve is required in place of the manufacturer's
recommendations for the instrumentation, unless those recommendations require more than three
points within the linear range. The lowest standard should not be greater than 10 times the
detection limit.
Next, determine the linear dynamic range (LDR) for the initial calibration. During the analysis,
if the concentration of a sample falls above the LDR, two options are available. The first option is
to dilute and reanalyze the sample. In this case, the diluent should have the same matrix as the
sample matrix The second option is to calibrate two concentration ranges. Samples are first
analyzed on the lower concentration range. Any samples for which the concentrations exceed the
upper end of the LDR are then reanalyzed on the higher concentration range. If this latter option
is performed, separate QC check samples (QCCSs) must be analyzed and reported for each range.
-------
Table 3-1. Summary of Internal Quality Control
Parameter
Procedure
Control Limits Corrective Action
Moisture
Laboratory Triplicate Analysis
Prepare and analyze two addi-
tional subsamples of one sample
in each batch.
Meet precision limits in Table 3-3.
Prepare and analyze two samples
in each batch in triplicate. If not
within control limits, check
temperature stability of the oven
and repeat triplicate analyses.
Particle Size Analysis
Quality Control Audit Sample
(QCASl
One QCAS of known concentration
is run in each batch.
Calibration and Standardization
Analyze a QCCS with each group
of soils.
QCAS must fall within accuracy
windows provided by QA manager.
Meets precision limits in Table 3-3.
Check the system for source of
error and reanalyze the QCAS and
associated samples.
Recalibrate balance, volumetric
pipet, and thermometer. Check
water bath or room temperature.
Then reanalyze QCCS and samples
bracketed by the affected QCCS.
Laboratory Duplicate Analysis
Prepare and analyze a second
subsample of one sample in every
batch.
Meets precision limits in Table 3-3.
Prepare and analyze two samples
in each batch in duplicate. If
either is outside the precision
limits, determine the source of
imprecision.
Quality Control Audit Sample
One QCAS of known concentration
is run in each batch.
QCAS must fall within accuracy
windows provided by QA manager.
Check the system for source of
error and reanalyze the QCAS and
associated samples.
(continued)
TJ O
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O ^
01
o
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CO
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Table 3-1. Continued
Parameter
Procedure
Control Limits Corrective Action
Soil pH
Calibration and Standardization
Calibrate pH meter for the range of
pH expected in the soil (usually pH
= 4 and pH = 7 standards).
Analyze a QCCS immediately after
calibration and after analyzing
every 10 or fewer samples.
Tire value of the QCCS must be
4.00 ± 0.05 and 7.00 ± 0.05.
Analyze one reagent blank of each
suspension solution.
Laboratory Triplicate Analysis
Prepare and analyze two additional
subsamples of one sample in every
batch.
Quality Control Audit Sample
One QCAS of known concentration
is run in each batch.
The value should be between pH >
4.5 and 7.5.
Meets precision limits in Table 3-3.
QCAS must fall within accuracy
windows provided by QA manager.
Recalibrate pH meter and
reanalyze fresh QCCS.
Check wiring, static electricity, and
solution level in electrode, then
reanalyze fresh QCCS.
Perform electronic checkout (see
section 6.4.4 or 10.4.4)
Replace electrode or pH meter,
then reanalyze fresh QCCS.
Determine source of contamination.
Prepare new solutions for
reanalysis of batch.
Prepare and analyze two samples
in each batch in triplicate. If either
is outside the precision limits,
check for contamination in the
suspension solution. Prepare new
solutions, reanalyze the batch.
Check the system for source of
error and reanalyze the QCAS and
associated samples.
(continued)
T) O3CO
Q> Q) O
-------
Table 3-1. (Continued)
Parameter
Procedure
Control Limits Corrective Action
Cation Exchange Capacity (CEC)
Calibration and Standardization for
Distillation/Titration Method
Acid for titration must
restandardized weekly.
be
Calculate instrument detection limit
based upon a minimum titration,
i.e., smallest possible volume, and
normality of acid.
Analyze a DL-QCCS.
Calibration blanks (0 mg/L
standard) are run before the 1st
sample, after every 10 samples,
and after the last sample. Three
reagent blanks (reagents carried
through the analytical procedure)
are analyzed per batch.
QCCS must be run every 10 or
fewer samples.
Laboratory Duplicate Analysis
Prepare and analyze a second
subsample of one sample in each
batch for each saturating solution.
Normality of acid should not
change more than 5%.
Meets detection limit in Table 3-2.
Value must be within 20% of the
theoretical concentration.
Blank should be less than CROL in
Table 3-2.
Measure each CEC and plot the
results on a control chart. Develop
95% and 99% confidence limits.
Required % RSD is 10%.
Meets precision limits in Table 3-3.
Prepare new solution.
Use a more dilute titrant.
Identify and correct problem.
Acceptable result must ba
obtained prior to sample analysis.
Investigate and eliminate source of
contamination, then reanalyze all
samples associated with the high
blanks.
Recalibrate. Analyze a second
QCCS and all samples bracketed
by the affected QCCS.
Prepare and analyze two samples
in each batch in duplicate. If
either is outside the precision
limits, check for contamination.
Recalibrate the balance, sample
diluter, flow injection analyzer
(FIA), or titrator. Reanalyze the
batch.
(continued)
-------
Table 3-1. (Continued)
Parameter
Procedure
Control Limits Corrective Action
Cation Exchange Capacity
(continued)
Cations - Ca, Mg, K, Na, Fe, Al, and
Si
Quality Control Audit Sample
One OCAS of known concentration
is run in each batch.
Calibration and Standardization
Calibrate the spectrometer as
required in the analytical method.
Analyze a QCCS immediately after
calibration, after every 10 or fewer
samples, and after the last sample
of the batch.
Verify calibration linearity.
Determine linear dynamic range.
Determine the instrument detection
limits.
Analyze a DL-QCCS.
QCAS must fall within accuracy
windows provided by QA manager.
Calculate the QCCS value from
calibration curve and plot result on
a control chart. Develop the 95%
and 99% confidence limits.
Acceptable range is ±10%.
Linearity as determined by a least-
squares fit should not be less than
0.99.
Meets the detection limits in Table
3-2.
Value must be within 20% of the
theoretical concentration.
Check the system for source of
error and reanalyze the QCAS and
associated samples.
Recalibrate Instrument. Prepare
new stock and calibration
standards if necessary. Analyze a
second QCCS and all samples
bracketed by the affected QCCS.
Check calibration standards to see
if properly prepared. Prepare new
stock and calibration standards if
necessary, and recalibrate. Follow
instrument manufacturer's trouble-
shooting procedures.
Check for possible contamination.
Optimize instrumentation, e.g.,
wavelength, burner or torch
position, oxidant and fuel
pressures, nebulizer flow rate,
integrity or impact bead or spoiler,
optical alignment.
Identify and correct problem.
Acceptable result must be
obtained prior to sample analysis.
(continued)
-------
Table 3-1. (Continued)
Parameter
Procedure
Control Limits Corrective Action
Cations - Ca, Mg, K, Na, Fe, Al. and
Si (continued)
Exchangeable Acidity - BaCL-TEA
Calibration blanks (0 mg/L
standard) are analyzed before the
1st sample, after every 10 samples,
and after the last sample of each
batch. Three reagent blanks (any
necessary reagents carried through
the analytical procedure) are run
per batch.
Analyze one spike per batch for all
required parameters.
Analyze one spike per batch for
calcium chloride extraction.
Laboratory Duplicate Analysis
Analyze a second subsample of
one sample in each batch for each
analyte.
Quality Control Audit Sample
One QCAS of known concentration
is run in each batch.
Calibration and Standardization
The solutions used for titration
must be restandardized weekly.
Blanks should be less than CRDL
in Table 3-2. The calcium value
should fall between 76 and 84
mg/L calcium.
Spike recovery should be within 90-
110% of known value.
Value for calcium should be
between 76 and 84 mg/L.
Meets precision limits in Table 3-3.
QCAS must fall within accuracy
windows provided by QA manager.
Normality of solution should not
change more than 5%.
Investigate and eliminate source of
contamination, then reanalyze all
samples associated with the high
blank.
Analyze two additional spike
samples; if either recovery does
not fall within 90-110% of known
value, notify QA manager before
reporting data.
Prepare fresh extraction solution.
Prepare and analyze two samples
in each batch in duplicate. If
either is outside the precision
limits, eliminate the source of
imprecision. Reanalyze the batch.
Check the system for source of
error and reanalyze the QCAS and
associated samples.
Prepare new solution.
(continued)
•003 Q?
0) 0) CD u>
*S||
-------
Table 3-1. (Continued)
Parameter
Procedure
Control Limits Corrective Action
Exchangeable Acidity - BaCI2-TEA
(continued)
Sulfate Isotherms and Extractable
Sulfate
Calibration and Standardization
Calculate instrument detection
limit, based upon a minimum
titration (i.e., smallest possible
volume, and normality of titrants).
Calibration blanks are analyzed
before the 1st sample, after every
10 samples, and after the last
sample of each batch. Three
reagent blanks per batch are
required.
Laboratory Duplicate Analysis
Prepare and analyze a second
subsample of one sample in each
batch.
Quality Control Audit Sample
One QCAS of known concentration
is run in each batch.
Calibration and Standardization
Verify calibration linearity.
Determine linear dynamic range.
Meets detection limit in Table 3-2.
Blanks should have concentrations
between 1.3 and 1.8 meq/L.
Meets precision limits in Table 3-3.
OCAS must fall within accuracy
windows provided by QA manager.
Linearity as determined by a least-
squares fit should not be less than
0.99.
Use more dilute titrants.
Determine and eliminate source of
variation, then reanalyze the batch.
Prepare and analyze two samples
in each batch in duplicate. If either
is outside the precision limits,
determine source of imprecision.
Reanalyze the batch.
Check the system for source of
error and reanalyze the QCAS and
associated samples.
Check calibration standards, see if
properly prepared. Prepare new
calibration standards, if necessary,
and recalibrate. Follow instrument
manufacturer's troubleshooting
procedures.
(continued)
"0 O 33 W
0) Q) CD (D
(Q •-+ < O
O ?> £' g-
owl'3
-------
Table 3-1. (Continued)
Parameter
Procedure
Control Limits Corrective Action
Sulfate Isotherms and Extractable
Sulfate (continued)
Calibrate as required in the
analytical methods. Analyze a
QCCS immediately after calibration
and after analysis of every 10 or
fewer samples.
Determine instrument detection
limits.
Analyze a DL-QCCS for both
extracts and the "0" isotherm.
Calibration blanks (0 mg/L
standard) are analyzed before the
1st sample, after every 10 samples,
and after the last sample of each
batch. Three reagent blanks
(necessary reagents carried
through the analytical procedure)
are analyzed per analytical batch.
Analyze one spike sample per
batch for both sulfate extracts.
Spike two separate soil samples
per batch with 2,8, and 32 mg S/L.
Analyze spike solution.
Calculate the QCCS value from the
calibration curve and plot result on
a control chart. Develop the 95%
and 99% confidence limits.
Acceptable range is ±5%.
Meets detection limits in Table 3-2.
Value must be within 20% of the
known concentration.
Blanks should be less than CRDL
in Table 3-2 and within 5% of the
required concentration for the other
isotherms.
Spike recovery is within 95-105% of
known value.
Spike recovery is within 95-105% of
known value.
Values should be less than CRDL
for O'mg/L, ±3% for 2,4,8 and 16
mg S/L, and ±2% for 32 mg S/L of
known concentration.
Recalibrate instrument. Prepare
new stock and calibration
standards, if necessary. Analyze a
second QCCS and all samples
bracketed by the affected QCCS.
Check for possible contamination.
Optimize instrumentation.
Identify and correct problem.
Acceptable results must be
obtained prior to sample analysis.
Investigate and eliminate source of
contamination, then reanalyze all
samples associated with the high
blank. Prepare new isotherm
solutions for solutions not meeting
the criteria.
Analyze two additional spike
samples; if either recovery does
not fall within 95-105% of known
value, notify QA manager before
reporting data.
Analyze two additional spike
samples; if either recovery does
not fall within 95-105% of known
value, notify QA manager before
reporting data.
Prepare fresh extraction solution.
(continued)
TJD
Q> Q)
3J CO
CD CD
8
»§§
<§°g
-------
Table 3-1. (Continued)
Parameter
Procedure
Control Limits Corrective Action
Sulfate Isotherms and Extractable
Sulfate (continued)
Total C,N, and S
Resolution Check
Once per analytical run (day) check
resolution of the anion separator
column by analyzing standards
containing sulfate (1 mg S/L) and
phosphate (1 mg P/L) or sulfate
and nitrate. Set instrument for a
nearly full-scale response on the
most sensitive range used.
Quality Control Audit Sample
One QCAS of known concentration
is run in each batch.
Laboratory Duplicate Analysis
Prepare and analyze a second
subsample of one sample in each
batch.
Calibration and Sample Analysis
Calibrate and standardize
combustion furnace as described in
method. Analyze a QCCS
immediately after calibration and
after analysis of every 10 or fewer
samples.
Resolution must exceed 60%.
QCAS must fall within accuracy
windows provided by QA manager.
Meets precision limits in Table 3-3.
Measure analyte and plot result on
a control chart. Develop the 95%
and 99% confidence limits (warning
and control). Precision should be
within limits outlined in Table 3-3.
Clean or replace anion separator
column, then repeat calibration and
resolution check. The eluent may
also be adjusted as needed.
Check the system for source of
error and reanalyze the OCAS and
associated samples.
Prepare and analyze two samples
in each batch in duplicate. If
either is outside the precision
limits, determine source of
imprecision. Reanalyze the batch.
Determine and correct problem.
Recalibrate and then analyze a
second QCCS and all samples
bracketed by the affected QCCS.
(continued)
TJ U 3J CO
0) 0) CD CD
(Q J-» < O
10 00
-------
Table 3-1. (Continued)
Parameter Procedure
Control Limits Corrective Action
Total C,N, and S (continued)
Verify calibration linearity.
Determine linear dynamic range.
Determine and establish IDL before
initial routine analyses. The IDL
equals 3 times the standard
deviation of 10 nonconsecutive
blank analyses.
Analyze one DL-QCCS per batch
with concentrations 2 to 3 times
the CRDL.
Matrix Spike
To one sample per batch uniformly
add a standard amount of analyte
at the endogenous level or 10 times
the instrumental detection limit,
whichever is greater.
Reagent Blanks
Analyze one reagent blank per
batch for each analyte.
Calibration blanks should be
analyzed before the 1st sample,
after every 10 samples, and after
the last sample of each batch.
Linearity as determined by a least-
squares fit should not be less than
0.99.
The IDL should be less than the
CRDL in Table 3-2.
Measured value must be within
20% of the theoretical
concentration. Plot concentration
on a control chart and submit
charts to the QA manager.
Calculate the percent recovery.
Acceptable range is 100 ± 10%.
The reagent blank should be less
than the CRDL in Table 3-2.
Calibration blanks should be less
than the CRDL in Table 3-2.
Check calibration standards to see
if properly prepared. Prepare new
stock and calibration standards, if
necessary. Recalibrate. Follow
instrument manufacturer's
troubleshooting procedures.
Check instrumental performance
using manufacturer specifications
and troubleshooting guide.
Recalibrate instalment and repeat.
Identify and correct problem,
obtain acceptable result before
continuing sample analysis.
Reanalyze all affected samples.
Repeat on two additional samples.
If possible, determine and
eliminate the source of the
interference, then repeat analyses.
If either or both are outside the
control limits, analyze the batch by
the method of standard additions.
Determine the source of error.
Prepare new blank for reanalysis of
batch.
Determine the source of error and
reanalyze the affected samples.
(continued)
TJ03JCO
SO SO CD
-------
Table 3-1. (Continued)
Parameter Procedure Control Limits Corrective Action
Total C, N, and S (continued) laboratory Duplicate Analysis
Prepare and analyze a second Precision should be within limits Prepare and analyze two samples
portion of one sample in every established in Table 3-3. in duplicate. If these fall outside
batch for each procedure. the range, check for source of
error. Recalibrate the instrument,
then reanalyze the batch.
Quality Control Audit Sample
Analyze the OCAS specified on the Measured concentration must fall Check instrument troubleshooting
shipping form. within windows given for that procedures. Recalibrate and
sample. analyze all associated samples.
T) O 3JCO
0) Q) (D CD
o cB
-* o
-------
Table 3-2. Contract-Required Detection Limits, Reporting Units, and Expected Ranges
Parameter
MOIST
SAND
SILT
CLAY
PH H2O
PH 002M
PH_01M
CEC OAC
CEC~CL
AC_BACL
CA OAC
MG OAC
K OAC
NA_OAC
CA CL
MG~CL
K Cl
NA CL
AL_CL
CA CL2
MGCL2
KCL2
NACL2
FECL2
ALICL2
FEPYP
AL>YP
FE'AO
AL'AO
SIAO
FE'CD
AL^CD
SO4H2O
SO4"PO4
SO4~0
SO4~2
SO4 4
SO4~8
SO4"16
SO4_32
CTOT
N'TOT
S'TOT
CRDL*
Calculated
(mg/L) Reporting Unit"
..«.
—
—
—
—
—
1.05d/0.0075*
1.05d/0.0075*
0.005 meq
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.10
0.50
0.05
0.05
0.05
0.10
0.10
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.010
0.005
0.001
wt. %
wt. %
wt. %
wt. %
pH units
pH units
pH units
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
meq/100g
wt. %
wt. %
wt. %
wt. %
wt. %
wt. %
wt. %
mg S/kg
mg S/kg
mg S/L
mg S/L
mg S/L
mg S/L
mg S/L
mg S/L
wt. %
wt. %
wt. %
Section 3.0
Revision 0
Date: 8/90
Page 15 of 20
Expected Range (Median)6
Mineral Samples
0.1-2.5
8.0-96.0 (59.5)
0.7-58.2 (28.3)
0.0-21.0 (7.1)
3.5-6.0 (5.0)
3.1-5.7 (4.5)
2.9-5.5 (4.4)
0.4-36.9 (9.2)
0.3-17.5 (5.4)
0.0-48.4 (9.0)
0.0-4.3 (0.17)
0.0-0.9 (0.08)
0.0-0.2 (0.07)
0.0-0.1 (0.02)
0.0-4.9 (0.17)
0.0-0.9 (0.08)
0.0-0.2 (0.07)
0.0-0.1 (0.02)
0.0-0.5
0.2-0.8 (0.5)
0.0-0.2 (0.04)
0.0-0.05 (0.01)
0.0-0.06 (0.02)
0.0-0.04 (0.01)
0.0-0.2 (0.01)
0.0-1.2 (0.2)
0.0-1.1 (0.2)
0.0-1.7 (0.3)
0.0-2.0 (0.3)
0.0-2.0
0.0-2.3 (1.0)
0.0-1.3 (0.3)
1.1-19.5 (7.6)
0.2-87.5 (26.0)
0.1-3.3 (0.76)
0.9-4.8 (2.2)
1.7-6.5 (3.7)
3.1-10.3 (6.9)
6.5-17.8 (13.4)
15.3-33.4 (27.5)
0.0-7.6 (0.8)
0.0-0.4 (0.05)
0.0-0.1 (0.01)
Organic Samples
1.3-6.0
—
—
—
2.9-5.3 (3.9)
2.7-5.0 (3.5)
2.4-4.8 (3.2)
21.8-147.5 (91.3)
9.6-60.2 (33.3)
24.6-153.2 (88.2)
0.3-49.4 (6.6)
0.1-7.7 (2.0)
0.0-1.9 (0.8)
0.0-0.8 (0.2)
0.8-37.2 (8.8)
0.1-7.9 (2.1)
0.1-1.9 (0.7)
0.0-0.8 (0.2)
0.0-1.0
0.5-4.2 (2.2)
0.0-1.4 (0.7)
0.0-1.0 (0.4)
0.0-0.4 (0.1)
0.0-0.2 (0.03)
0.0-0.6 (0.2)
0.0-1.0 (0.2)
0.0-1.0 (0.2)
0.0-1.1 (0.2)
0.0-1.1 (0.2)
0.0-1.0
0.0-1.2 (0.3)
0.0-0.9 (0.2)
8.0-74.1 (44.3)
9.8-167.3 (45.6)
~-
_
5.1-53.8 (38.0)
0.2-2.1 (1.4)
0.0-0.5 (0.17)
'Contract-required detection limit.
All values determined on an oven-dry soil weight basis.
'Expected ranges in mg/L of reported data values for mineral and organic samples, based on the 1st, 50th, and 95th
percentiles of data from previous DDRP surveys. Ranges for MOIST, AL_CL, and SI AO parameters are anticipated.
For flow injection analysis (FIA) method, in mg/L.
*For titration method, in meq units.
-------
Section 3.0
Revision 0
Date: 8/90
Page 16 of 20
Spectroscopic-grade or high purity chemicals are recommended for primary standards when
analysis is done by atomic absorption or emission methods. Also, calibration standards should
have the same matrix as the solutions being analyzed.
3.2.3 Blanks
3.2.3.1 Calibration Blanks-
Analyze a calibration blank at the start of each analysis run, at specified intervals thereafter
(e.g., after every ten samples), and after the last sample to check for baseline drift. The calibration
blank is defined as a "0" mg/L standard and contains only the matrix of the calibration standards.
The observed concentration of each calibration blank should be less than or equal to the CRDL (see
Table 3-2). If it is not, rezero the instrument and recheck the calibration.
3.2.3.2 Reagent Blanks-
For methods that require exchange or extraction, prepare and analyze the recommended
number (usually three) of reagent blanks for each group of samples processed. If three are run,
they should be placed near the beginning, the middle, and the end of the batch. A reagent blank
is composed of all reagents in the same quantities used in preparing an actual sample for analysis.
The reagent blank undergoes the same digestion or extraction procedures as an actual sample. The
concentration of each reagent blank should be less than or equal to the CRDL If the concentration
exceeds this limit, the source of contamination should be investigated and eliminated. A new
reagent blank is then prepared and analyzed, and the same criteria are applied. All samples
associated with the "high" blank should be reprocessed and reanalyzed after the contamination has
been eliminated.
3.2.4 Replicate Sample Analysis
Prepare and analyze a soil sample from each batch in duplicate for each parameter; log all
information on the appropriate QC form. (Some procedures recommend triplicate analysis. Refer
to the specific method sections for guidance.)
For values above the cutoff level in Table 3-3, calculate the standard coefficient of variation
or percent relative standard deviation (%RSD) as follows:
%RSD = (s/x) x 100
where s is the standard deviation calculated for (n-1) degrees of freedom and X is the mean of the
replicate samples. For values below the cutoff, calculate the standard deviation. The %RSD and
standard deviation should be plotted on control charts.
If the duplicate values fall outside the precision limits outlined in Table 3-3, an explanation
should be sought (e.g., instrument malfunction or calibration drift). A second sample in the batch
should then be prepared and analyzed in duplicate. No additional samples should be analyzed until
all duplicate sample results are within the control limits.
-------
Table 3-3. Intralaboratory Precltlon Goal* for Laboratory Replicate*
Section 3.0
Revision 0
Date: 8/90
Page 17 of 20
Precision Limits*
Parameter
MOIST
SAND
SILT
CLAY
PH H20
PH~002M
PHJJ1M
CEC OAC
CEC'CL
AC.BACL
CAOAC
MG'OAC
KOAC
NA.OAC
CACL
MG'CL
KCL
NACL
AL.CL
CACL2
MG"CL2
KC"L2
NACL2
FECL2
ALCL2
FEPYP
AL'PYP
FE'AO
AL'AO
SIAO
FE'CD
AL^CD
S04 H2O
S04 PO4
SO4~0
S04~2
S04~4
S04'8
SO4"16
S04.32
CTOT
N'TOT
S'TOT
Cutoff
12.0
—
_
—
_
—
—
2.5
2.5
6.7
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
1.3
1.0
0.05
0.05
0.05
0.07
0.33
0.3
0.3
0.3
0.3
0.3
0.3
0.3
15.0
15.0
2.0
2.0
2.0
2.0
2.0
2.0
0.05
0.15
0.02
Mineral Samoles
Lower(SD)
0.3 wt %
3.0 wt %
3.0 wt %
2.0 wt %
0.10 unit
0.10 unit
0.10 unit
0.25 meq/100g
0.25 meq/100g
1.0 meq/100g
0.02 meq/100g
0.02 meq/100g
0.02 meq/100g
0.02 meq/100g
0.02 meq/100g
0.02 meq/100g
0.02 meq/100g
0.02 meq/100g
0.2 meq/100g
0.05 meq/100g
0.005 meq/100g
0.005 meq/100g
0.005 meq/100g
0.01 meq/100g
0.05 meq/100g
0.03 wt %
0.03 wt %
0.03 wt %
0.03 wt %
0.03 wt %
0.03 Wt %
0.03 wt %
1.5 mg S/kg
1.5 mg S/kg
0.1 mg S/L
0.1 mg S/L
0.1 mg S/L
0.1 mg S/L
0.1 mg S/L
0.1 mg S/L
0.05 wt. %
0.015 wt. %
0.002 wt. %
Oraanic Samoles
Upper(RSD)
2.5%
—
—
—
_
—
—
10%
10%
15%
10%
10%
10%
10%
10%
10%
10%
10%
15%
5%
10%
10%
10%
15%
15%
10%
10%
10%
10%
10%
10%
10%
10%
10%
5%
5%
5%
5%
5%
5%
10%
10%
10%
Cutoff
12.0
_
_
—
«
_
—
2.5
2.5
6.7
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
3.3
4.0
0.5
0.25
0.25
0.33
1.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
15.0
15.0
—
—
—
—
—
—
0.5
0.15
0.02
Lower(SD)
0.3 wt %
™ _
_ _
._ _
0.10 unit
0.10 unit
0.10 unit
0.25 meq/100g
0.25 meq/100g
1.0 meq/100g
0.1 meq/100g
0.1 meq/IOOg
0.1 meq/100g
0.1 meq/100g
0.1 meq/100g
0.1 meq/100g
0.1 meq/100g
0.1 meq/100g
0.5 meq/100g
0.2 meq/100g
0.05 meq/100g
0.025 meq/100g
0.025 meq/100g
0.05 meq/100g
0.2 meq/100g
0.03 wt %
0.03 wt %
0.03 wt %
0.03 wt %
0.03 wt %
0.03 wt %
0.03 wt %
1.5 mg S/kg
1.5 mg S/kg
._ _
— —
— —
— -_
— — —
— —
0.05 wt. %
0.015 wt. %
0.002 wt. %
Upper(RSD)
2.5%
__
_
—
10%
10%
15%
10%
10%
10%
10%
10%
10%
10%
10%
15%
5%
10%
10%
10%
15%
15%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
'Precision objectives based on a concentration cutoff value, where the standard deviation is used for lower
concentrations and the percent relative standard deviation is used for higher concentrations.
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3.2.5 Quality Control Standards
Two QC standards are recommended. A detection limit QC check sample (DL-QCCS) is used
to assess the validity of data near the detection limit. A QCCS is used to assess the validity of
data in the mid-calibration range. Control charts must be kept for the QCCS.
DL-QCCS Standards~tx\a\yz& one DL-QCCS per batch. This is a low-level QC standard that
contains the analyte of interest at a concentration two to three times above the CRDL Log in all
information on the appropriate QC form. The purpose of the DL-QCCS is to eliminate the necessity
of formally determining the IDL at frequencies less than every 30 days or on a per batch basis.
QCCS Standards~Immed\ale\y after standardization of an instrument, analyze a QCCS
containing the analyte of interest at a concentration in the mid-calibration range. Log in all
information on the appropriate QC form. QCCS standards may be obtained commercially or may
be prepared by the analyst from a source which is independent of the calibration standards. The
QCCS is analyzed to verify the calibration curve prior to any sample analysis, after every 10 samples,
and after the last sample in the batch.
Establish warning and control limits (i.e., the 95 and 99 percent confidence intervals). A value
outside the 99 percent confidence interval is unacceptable. When an unacceptable value for the
QCCS is obtained, recalibrate the instrument and reanalyze all samples up to the last acceptable
QCCS.
At specified intervals determined by the QA program, the control charts should be updated.
Cumulative means and new warning and control limits should be calculated. Bias for a given
analysis is indicated by at least seven successive points on one side of the cumulative mean. If
bias is indicated, analysis should be stopped until an explanation is found. The same QCCS should
be used to establish all values on a given control chart to ensure continuity. Data from the QCCS
standards should be logged on the appropriate QC forms.
3.2.6 Matrix Spikes
Matrix spikes are prepared for each extract or exchange procedure as listed in Table 3-1 and
as described in the individual methods sections.
The sample selected for spiking should be of mid-range concentration. The spike recovery
should be within 90 to 110 percent (95 to 105 percent for sulfate isotherms) of the known value of
the spike. If this criterion is not met, two additional, different samples from the batch should be
spiked and analyzed, and logged on the same QC form. If the spike recovery of either of the two
additional samples fails to meet the 90 to 110 percent criterion (95 to 105 percent for sulfate
isotherms), the laboratory or QA manager should be notified before the data for this parameter are
reported.
For soil extract or exchange solutions, a matrix spike is prepared by spiking an aliquot of an
extract solution with a known quantity of analyte prior to analysis. The calculated concentration of
the added spike should be approximately equal to the endogenous level of the aliquot or 10 times
the detection limit, whichever is larger, and should not exceed the linear range of the instrument.
Also, the volume of the spike should be negligible in calculating the spike recovery. The spiked
sample is analyzed side by side in the batch with the sample that was aliquoted.
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3.2.7 Ion Chromatography Resolution
Perform an ion Chromatography (1C) resolution test once per analytical run by analyzing a
standard that contains sulfate, nitrate, and phosphate in concentrations that approximate those
found in the 1C analysis. If the resolution does not exceed 60 percent, the column should be
replaced, and the resolution test should be repeated.
3.2.8 Quality Control Audit Sample
One QC audit sample (QCAS) of known concentration is run in each batch. Data from the
QCAS should fall within the defined accuracy windows for the specific audit materials.
3.3 Data Entry and Record Keeping
3.3.1 Raw Data
All instrument print-outs, strip-charts, etc., should be identified with the following information:
date and analyst's name, laboratory method and specific parameter measured, and batch and
sample number. These raw data should be retained by the laboratory for ready retrieval as directed
by the QA manager.
All observations made in the laboratory (i.e., weighings, extract volumes, and titrations) should
be recorded in an appropriate log book or data sheet along with the above information required for
instrument print-outs as well as all information required for calculations, e.g. (aliquot and final
volumes) and all appropriate QC data as discussed in the preceding section. These log books or
data sheets should be retained by the laboratory for ready retrieval as directed by the QA manager.
3.3.2 Reported Data
All required data should be reported to the recommended number of decimal places as
indicated on the reporting forms. Copies of the data forms are provided in Appendix B.
Any data obtained using deviations from the established procedures should be tagged with
the appropriate data qualifier (Table 3-4 lists data qualifiers developed for the DDRP). A detailed
explanation of the deviation used to acquire the tagged data should accompany that data.
Table 3-4. Analytical Laboratory Data Qualifiers (Tags)
Data Qualifier (Tag) Explanation
A Instrument unstable.
B Redone, first reading not acceptable,
F Result outside criteria with consent of QA manager.
G Result obtained from method of standard additions.
J Result not available; insufficient sample volume shipped
to laboratory.
(continued)
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Data Qualifier (Tag) Explanation
L Result not available because of inter rence.
M Result not available; sample lost or destroyed by
laboratory.
N Result outside QA criteria.
P Result outside criteria, but insufficient volume for reanalysis.
R Result from reanalysis.
S Contamination suspected.
T Container broken.
U Result not required by procedure; unnecessary.
X No sample.
Y Available for miscellaneous comments.
Z Result from approved alternative method.
3.4 References
Blume, L. J., M. L Papp, K. A. Cappo, J. K. Bartz, D. S. Coffey, and K. Thorton. 1987a. Sampling
Protocols lor the Southern Blue Ridge Province Soil Survey. Appendix A In: Coffey, D. S., J.
J. Lee, J. K. Bartz, R. D. Van Remortel, M. L Papp, and G. R. Holdren. Direct/Delayed Response
Project: Field Operations and Quality Assurance Report for Soil Sampling and Preparation in
the Southern Blue Ridge Province of the United States Volume I: Sampling. EPA/600/4-
87/041a. U.S. Environmental Protection Agency, Office of Research and Development,
Washington, D.C.
Blume, L. J., D. S. Coffey, and K. Thornton. 1987b. Field Sampling Manual for the National Acid
Deposition Soil Survey. Appendix A In: Coffey, D. S., M. L. Papp, J. K. Bartz, R. D. Van
Remortel, J. J. Lee, D. A. Lammers, M. G. Johnson, and G. R. Holdren. Direct/Delayed
Response Project: Field Operations and Quality Assurance Report for Soil Sampling and
Preparation in the Northeastern United States. Volume I: Sampling. EPA/600/4-87/030. U.S.
Environmental Protection Agency, Office of Research and Development, Washington, D.C.
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4.0 Sample Processing and Rock
Fragment Determination
4.1 Overview
Sample processing includes sample drying, disaggregation, sieving, homogenization, and
subsampling. Each of these is performed as sample processing steps in the preparation laboratory;
homogenization and subsampling are also completed at the analytical laboratory. The objective of
these procedures is to produce homogeneous subsamples for subsequent analyses of physical and
chemical parameters. Also included in this section is the procedure used for determination of
percent rock fragments.
The procedures presented here are specific to bulk sample preparation methods employed in
the DDRP. Alternatives to these procedures are available in the published literature; for example,
Procedures for Collecting Soil Samples and Methods of Analysis for Soil Surveys (USD A/SCS, 1972).
Alternatives include, but are not restricted to, use of different sized sieves, determination of soil
moisture on a subsample of sieved, but not air-dry, sample, different size classifications of rock
fragments, and grinding of soil material to pass a No. 60 or No. 100 sieve.
4.1.1 Summary of Method
Sample tables constructed of polyvinyl chloride (PVC) and heavy nylon mesh are used to air
dry the samples. Use of the mesh enhances air circulation and increases the rate of sample drying.
After a bulk soil sample has been determined to be air dry, it is ready to be disaggregated and
sieved to remove rock fragments and to prepare the sample for homogenization and subsampling.
The disaggregation and sieving areas should be covered with protective layers of kraft paper and
cleaned after each sample has been sieved. Dust masks and protective clothing should be worn
at all times. Ventilation and heating should be provided in the sieving area.
To obtain representative volumes of soil suitable for detailed analysis at the analytical
laboratories, it is necessary to prepare homogenous subsamples from the less than 2-mm soil
fraction through the use of a riffle splitter. The preparation laboratory prepares two different
subsamples for: (1) analyses of physical and chemical parameters and, (2) elemental analysis of
total carbon, nitrogen, and sulfur. The general analytical sample should weigh approximately 500
g, while the elemental analytical sample should weigh approximately 50 g. Each analytical sample
is derived through homogenization and subsampling by the procedure described in Section 4.6.3.
During shipping to the analytical laboratory, the sample material within each container
segregates by particle size and density. Therefore, each sample must be homogenized by thorough
mixing prior to removal of aliquots for analysis. Mixing should be performed by riffle-splitting.
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4.1.2 Interferences
The known interferences specific to the parameter being measured are detailed in the sections
containing analysis procedures for that parameter. In sample preparation, all interferences are
collectively termed contamination. Chemicals used in analyses are to be kept away from the drying
area. Food, drinks, and smoking are prohibited in the drying area. A separate pair of gloves should
be worn when handling each sample. The drying area should be damp-mopped at least once a
week to control dust.
A source of compressed air is necessary to clean the surfaces of the equipment (e.g., rolling
pins, sieves, and gloves) after processing each sample. However, because water and oil tend to
accumulate in the tank and conduit, the air must be passed through a filter trap to collect vapor and
liquid.
In addition to cleaning with compressed air, the surfaces of the processing equipment may
be wiped with clean Kimwipes if soil is adhering to the rolling pin or to the frame of the sieve. Used
tissues are discarded after each sample is processed to avoid contamination.
The riffle splitter is cleaned with compressed air after each sample is split. If the operator
suspects that the riffle splitter is still not thoroughly clean, the riffle splitter should be washed with
deionized water and allowed to air dry completely. The work area is cleaned with a brush or hand
vacuum after each sample is processed. The work area should be vented with an operating fume
hood.
4.1.3 Safety
The calibration standards, sample types, and most reagents pose little hazard to the analyst.
However, protective clothing (laboratory coat and gloves), safety glasses, and dust masks should
be worn.
4.2 Sample Collection, Preservation, and Storage
The procedures contained here are applicable to bulk soil samples (routine and duplicate) and
to field audit samples. Bulk samples are those soil samples taken from a designated portion of a
specific horizon. A bulk sample contains approximately one gallon of soil and generally weighs
about 5.5 kg. The bulk samples are deposited in large plastic bags and placed within protective
outer canvas bags. Field audit samples are quality evaluation (QE) samples; these samples are
sieved, packaged, and shipped in the same manner as their associated routine samples. All
samples should be stored at 4 'C.
4.3 Equipment and Supplies
4.3.1 Equipment Specifications
1. Riffle splitter, Jones-type; closed-bin, two-pan, 1.25-cm baffles (preparation laboratory).
2. Enclosed Drawer Riffle Sampler (American Society for Testing Materials [ASTM] D271) with
four drawers, Fisher Scientific No. 04-940 and 04-940-5, or equivalent. Larger-sized
splitters should not be used for this operation (analytical laboratory).
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4.3.2 Apparatus
1. Fume hood.
2. Drying tables, PVC/nylon mesh.
3. Rolling pin, wooden.
4. Rubber stoppers.
5. Brass sieves, square-holed: 2-mm and 4.75-mm.
6. Clean sieving table and work area.
7. Air compressor, with in-line filter.
8. Balance, capable of weighing to 0.1 g.
9. Wide-mouth funnel.
10. Distribution pan.
11. Brush or hand vacuum.
12. Balance calibration weights, 3-5 weights covering expected range.
4.3.3 Reagents and Consumable Materials
1. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
2. Kraft paper, 36" wide rolls.
3. Plastic gloves (unpowdered).
4. Small cellophane bags with twist ties.
5. Kimwipes.
6. Dust masks.
7. Nalgene bottles: 2-L, 500-mL, 125-mL
8. Plastic bottles, 500-mL, wide mouth.
9. Bulk sample processing raw data forms (Appendix B, Figure B-3).
10. DDRP Label A rolls (Figure 3-1).
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4.4 Calibration and Standardization
Calibration of the balance is detailed in Appendix A, General Laboratory Procedures.
4.5 Quality Control
The only quality control check applicable to this procedure is daily and weekly checks of the
balance accuracy using three to five balance calibration weights covering the range of sample
measurements.
4.6 Procedure
4.6.1 Sample Drying
1. Label a bulk sample processing raw data form (see Appendix B, Figure B-3) for each
sample to be air dried.
2. Place two fresh sheets of kraft paper, approximately 1 m x 1 m in area, on the mesh
partition of the drying table. With gloved hands, slowly spread the sample on top of the
sheets of paper, taking care not to lose any soil off the paper or contaminate any
adjacent samples.
NOTE: In some cases, samples may be received from the field in more than one
sample container (bag). Combine the contents of all containers comprising
a single sample.
3. Disaggregate any large pedons that impede the spreading of the sample over the entire
area of the paper. Place an additional sheet of kraft paper loosely over the sample.
4. Identify the sample by attaching the sample's processing raw data form to a hook
attached to the drying table or other mechanism. The original canvas and plastic
sampling bags should be kept on the floor beneath the sample as a second check on
sample identity.
NOTE: Immediately after a sample is spread to dry, field-moist pH is determined
(Section 6.0).
5. Daily, stir the soil sample with gloved hands to facilitate drying.
6. For the first few days that a wet sample is spread, the bottom sheet of paper may need
to be changed daily in order to alleviate excessive moisture accumulation. Any
observations of fungal or algal growth should be noted on the bulk sample processing
raw data form.
NOTE: Soils high in clay may harden nearly irreversibly if allowed to dry without a
preliminary disaggregation of medium and coarse pedons. An effort should
be made during the air-drying procedure to disaggregate these pedons by
physical manipulation with gloved hands while still somewhat moist or
friable, before reaching an air-dry state.
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7. Allow the sample to air dry until it is believed to be at or below the specified moisture
content. This process generally takes about two days, although drying time may vary
from one day to a week or more.
8. Subsample an aliquot for the air-dry moisture determination (Section 8.0).
4.6.2 Disaggregation and Sieving
A bulk sample must be weighed in its entirety before it is disaggregated and sieved in order
to properly calculate the percentage of rock fragments in the sample.
1. Weigh the bulk sample while still in its plastic bag to the nearest 0.1 g and record this
weight under "TOTAL BULK_WT" on the bulk sample processing raw data form. Large
pieces of stems, moss, twigs, or roots are to be removed from a mineral sample before
its bulk weight is determined.
2. Place a 1-m by 1-m sheet of kraft paper on top of the sieving table.
3. Place a 60-cm by 60-cm sheet of kraft paper on top of the table and spread small
portions of the bulk sample within the confines of the sheet. Carefully examine the nature
of the rock fragments within the sample and determine the amount of pressure to apply
to the sample to disaggregate the soil pedons without fracturing or crushing the
fragments.
4. Place another 60-cm by 60-cm layer of kraft paper over the sample and gently roll a
wooden rolling pin across the sample; enough force should be applied to break up the
pedons, but not so much that weathered rock fragments are crushed.
5. Place a portion of sample in the 2-mm mesh sieve and gent/ypush the soil through the
sieve with a rubber stopper. Attempt to include any soil adhering to rock fragments.
Remove and discard any small roots remaining on the sieve.
6. Continue sieving until all of the less than 2-mm soil has passed through the 2-mm sieve.
7. Save the less than 2-mm sample in a 2-L Nalgene bottle pre-labeled with a DDRP Label
A and place the bottle in cold storage until ready to proceed with homogenization and
subsampling (sections 4.63 and 4.6.4). Continue processing the remaining rock fragments
as described in Section 4.6.5.
4.6.3 Homogenization and Subsampling (Preparation Laboratory)
1. For each sample, pre-label one 500-mL and one 125-mL Nalgene bottle with the DDRP
Label A information.
2. Position the two receiving pans under the riffle splitter.
3. Pour all of the less than 2-mm soil from the 2-L Nalgene sample bottle evenly across the
baffles of the riffle splitter.
4. Transfer the soil from each receiving pan into the distribution pan and replace the
receiving pans under the riffle splitter.
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5. Repeat Step 4 five times in succession with the material in each receiving pan.
6. Pour the sample evenly across the baffles and place the soil from one receiving pan into
the 2-L bottle.
7. Transfer the soil in the other receiving pan to the distribution pan and continue splitting
as necessary until approximately 500 g of soil occupies one of the receiving pans.
8. Place the entire contents of the pan into the pre-labeled 500-mL bottle (general analytical
sample).
9. Repeat the splitting using the remaining soil until approximately 50 g of soil occupies one
of the receiving pans; transfer the entire contents of the pan into the pre-labeled 125-mL
bottle (elemental analytical sample).
10. Transfer all leftover soil into the 2-L bottle to serve as an archive sample. The analytical
samples are grouped by set ID and placed in cold storage until they are batched and
shipped via overnight express service to the analytical laboratories. The archive samples
are grouped by batch ID and remain in cold storage indefinitely.
4.6.4 Homogenization and Subsampling (Analytical Laboratory)
1. Pour the sample from the shipping bottle slowly and evenly across the slots of the
splitter, keeping the drop height less than 2 inches to avoid excessive loss of dust.
Repeat this procedure for 5 passes through the riffle splitter.
2. Place the split sample from one pan in the shipping bottle; label this as a laboratory
reference sample and refrigerate at 4 *C.
3. Place the split sample from the other pan in a clean Nalgene bottle, label, and use for
laboratory analysis.
NOTE: To mix the soil before removing an aliquot, the bottle should never be
more than three-fourths full.
NOTE: Thoroughly clean the splitter and pans to prevent sample carry-over from one
sample to the next.
After the sample has been homogenized, minimal bottle movement (transport, shaking, etc.)
is warranted to eliminate possible sample resegregation by particle size and density. Bottles must
remain closed (capped) at all times except during aliquot removal for each analysis. Bottles may
remain at room temperature while analyses are being performed. Removal of an aliquot for a given
analysis should be done by a random insertion of a clean sampler (spatula, scoop, etc.) into the
bottle.
NOTE: If the bottle will not be used for aliquot extraction for more than 7 days, storage of
the sample at 4 *C is required. Re-warm the sample to room temperature with the
bottle closed (capped) prior to further analysis.
After all analyses have been completed and the results have been checked, the analytical
samples are stored at 4 *C in the event that reanalysis is necessary.
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4.6.5 Rock Fragment Determination
1. Save the rock fragments which could not pass through the 2-mm sieve (Section 4.6.2) and
place them on the 4.75-mm sieve.
2. Retain in separate cellophane bags the material which passes through the 4.75-mm sieve
and that which does not pass.
NOTE: If field procedures do not include passing the sample through a 20-mm
sieve, pass the material which was retained on the 4.75-mm sieve through
a 20-mm sieve. Retain in a cellophane bag the material which passes the
20-mm sieve. Also retain and weigh the material which did not pass the 20-
mm sieve; subtract this value from the orginal total bulk weight. Use the
adjusted total bulk weight in Section 4.7.
3. Weigh to the nearest 0.1 g the fragments which passed through the 4.75-mm sieve but
were retained by the 2-mm sieve. Record this weight on the bulk sample processing raw
data form under "2- TO 4.75-MM ROCK FRAGMENTS". Then weigh the fragments that
were retained by the 4.75-mm sieve. Record this weight under "4.75- TO 20-MM ROCK
FRAGMENTS".
Place the rock fragment bags for each sample in the leftover plastic bag from the bulk sample.
Make sure that a DDRP Label A with the appropriate sample code and set ID is affixed to the bag.
Save all rock fragment bags, organized by set ID, until instructed by the soil sampling task leader
to discard or transfer the fragments to another location. It is not necessary to keep the rock
fragments in cold storage.
4.7 Percent Rock Fragment Calculations
The following calculations may be performed by computer calculation after the raw data are
entered. If so, it is still advantageous to manually check a few samples using these calculations
to understand the procedure and to test the accuracy of the computer program. The percentages
of fine gravel (RF_FG) and medium gravel (RF_MG) are calculated as follows:
_ 2- to 4.75-mm rock fragments
Total Bulk wt.
_ 4-75~to 20-mm rock fragments
Total Bulk wt.
4.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTMStandards, Vol. 11.01,
Standard Specification for Reagent Water, D-1193-77 (reapproved 1987). ASTM,
Philadelphia, Pennsylvania.
U.S. Department of Agriculture/Soil Conservation Service. 1972. Procedures for Collecting Soil
Samples and Methods of Analysis for Soil Surveys. Soil Survey Investigations Report
No. 1, United States Department of Agriculture, U.S. Government Printing Office,
Washington, D.C.
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5.0 Bulk Density Determination
5.1 Overview
Density is defined as weight per unit volume and is expressed in units of g/cm3. The bulk
density of a soil is defined as the weight of dry soil per unit volume including the pore space. For
mineral soils, bulk density generally ranges from 0.6 to 2.0 g/cm3. With increasing organic matter
content, soils generally exhibit a decrease in bulk density because organic matter has higher
porosity and lower density than mineral particles of the same diameter.
5.1. 1 Summary of Method
In the DDRP surveys, the clod method is the primary method for determining bulk density.
Where possible, three replicate clod samples are extracted from each horizon. The average bulk
density of the replicates is assumed to be the bulk density of that particular horizon. Analysis of
the clods is based on the method described in the USDA/SCS (1984), Kern and Lee (1989), and Kern
et at. (in preparation).
Two alternate methods are also presented for soil horizons that fail to yield satisfactory clods.
One method is volume replacement (VR), a method similar to one described by Flint and Childs
(1984), which utilizes a known volume of small foam beads packed into a cylinder to replace a
selected volume of soil excavated from a given horizon. Subtracting the initial from the final volume
yields the estimated volume of sample collected. The other method is a volume filling (VF) method
that is used if the clod or VR methods do not produce representative samples. The volume of this
type of sample is based on the absolute height of a 250-mL beaker, which is a constant 300 cm3.
The known volume samples are processed in a manner similar to the method described in Blake
5. /? interferences
evaporating dishes used in the clod method must be thoroughly cleaned after each use, as
their weights are pre-determined and used in the calculation of results. Tongs or finger cots should
be used when transferring the dishes from one location to another.
5.1.3 Safety
5.1.3.1 Clod Method-
Laboratory personnel should use caution when working around the muffle furnace because
temperatures of up to 450 *C are common. The furnace should be activated only in an operable
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fume hood. Heat resistant gloves may be needed when placing samples in the furnace. The
furnace must be adequately vented and protected from human contact and combustible materials.
Extra precaution must be taken in the use of the Saran powder and acetone solution (see
Section 5.3.2, Step 2). When mixed, the resulting solution has a tendency to volatilize hydrogen
chloride gas which can cause deleterious health effects. The solution should be used only in an
operating vented fume hood. Half mask and cartridge-type respiratory protection, gloves, and
laboratory coat should be worn.
In the field, exposure to Saran solution through inhalation and skin contact must be minimized.
Gloves and respiratory protection are recommended. Use solution only in a well-ventilated area
downwind of the sampling site.
5.1.3.2 Volume Methods-
The safety concerns cited above do not apply to the VR or VF methods. Protective clothing
(laboratory coat and gloves), safety glasses, and dust masks should be worn.
5.2 Sample Collection, Preservation, and Storage
Clod samples are fist-sized, structurally intact, bulk density samples taken from designated
horizons. In the field, each clod is wrapped in a hairnet and dipped briefly in a 1:5 Sararracetone
solution to help maintain the clod structure and reduce moisture loss from the clod during transport
and storage. Each clod is labeled, covered by a small plastic bag, and placed in a special box with
dividers.
Known volume bulk density samples are taken from horizons where clods are unobtainable.
There are two types of known volume samples used in the DDRP: volume replacement and volume
filling samples. These bulk density samples are packaged in small, pre-labeled plastic bags in much
the same manner as the bulk soil samples.
Samples are stored at 4 *C until analysis.
5.3 Equipment and Supplies
5.3.1 Apparatus
The following items are used in both the clod and volume methods:
1. Convection oven.
2. Desiccator and desiccant.
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3. Brass sieve, squared-holed, 2 mm.
4. Forceps.
The following additional apparatus is needed for the clod method:
1. Fume hood.
2. Balance, capable of weighing to 0.1 g.
3. Organic vapor mask, cartridge-type.
4. Beakers, 1000-mL and 2000-mL
5. Ring stand.
6. Test tube clip, adjustable.
7. Evaporating dishes, pre-numbered, tolerance to 450 *C.
8. Furnace gloves.
9. Tongs.
10. Muffle furnace.
11. One-gallon metal cans with airtight lids (paint cans).
12. Magnetic stirrer and stir bars, or long stir sticks.
13. Shower curtain rod.
14. Stop watch.
15. Thermometer, National Bureau of Standards (NBS)-traceable
16. Balance calibration weights, 3-5 weights covering expected range.
17. Class "P1 balance weight, 500 g.
The only item needed for the volume methods in addition to the four listed previously is:
1. Balance, capable of weighing to 0.01 g.
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5.3.2 Reagents
NOTE: All reagents listed are for the clod method. The volume methods do not require any
reagents.
1. Acetone, industrial grade.
2. Saran:acetone clod dipping mixture, approximately 1:5 by weight.
NOTE: The clod dipping solution must be mixed only under an operating vented
fume hood. The operator must wear a cartridge-type organic vapor mask
and laboratory coat while mixing the dipping solution.
For the DDRP, the Saran powder is prepackaged in 540-g allotments. One packet mixed
with approximately 3400 mL of acetone provides a nearly 1:5 by weight mixture resembling
light syrup. One-gallon paint containers are used for mixing and storing the solution.
Slowly add the contents of each packet to the acetone while stirring. Continue stirring
to ensure thorough dissolution of the powder. The solution normally is well mixed when
it has the color and consistency of amber syrup and there is no gummy Saran residue on
the edges or bottom of the container. If the solution is a milky color, additional mixing
is required. The powder has a tendency to precipitate and clump around a container's
lower rim when mixed with acetone. To prevent this, use a long stir stick and thoroughly
scrape the inner rims. If possible, use a magnetic stirrer and a stir bar to mix the
ingredients in a beaker until well blended, then transfer mixture to paint container for
storage.
After mixing the solution, the container should be capped as tightly as possible to prevent
leakage of the solution or evaporation of the acetone.
3. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
5.3.3 Consumable Materials
Consumable items required for the clod method are:
1. Paper bags, pre-labeled.
2. Plastic bags, large.
Consumable items required for the known volume methods are:
1. Paper bags, pre-labeled.
2. Clod bulk density raw data form (Appendix B, Figure B-4).
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3. Known volume bulk density raw data forms (Appendix B, Figure B-5).
4. Known volume log book (known volume method).
5. Volume data from sample receipt log book (known volume method).
5.4 Calibration and Standardization
Calibration of the balance is detailed in Appendix A, General Laboratory Procedures.
5.5 Quality Control
NOTE: This applies only to the clod method.
Record the dry weight and submerged weight of a 500-g Class "P1 balance weight immediately
before and after a run of samples. These weights are used to verify proper balance operation and
are charted on a daily basis.
5.6 Procedure
5.6.1 Clod Method
NOTE: All raw data obtained from the clod analysis are recorded on the clod bulk density
raw data form (see Appendix B, Figure B-4). For each clod to be analyzed, record
the set ID, sample code, and the replicate number on the form. Examine the label
attached to the clod and record the number of field dips performed by the
sampling crew under "FIELD_DP' on the form. Weigh the clod, without removing
the label, to the nearest 0.1 g and record this weight under "FIELD_WT/MOIST".
1. Suspend the clod in a convection oven and dry overnight at 105 *C for mineral samples,
or 60 *C for organic samples. The following morning, transfer the clod into a desiccator
for 30 minutes. Weigh the sample to the nearest 0.1 g and record this weight under
"FIELD_WT/DRY'.
2. Hang the clod on a suspended curtain rod within an operating vented fume hood. Dip the
clod into a container of 1:5 by weight Saran:acetone mixture (see Section 5.3.2, Step 2)
for three seconds and then allow the coating to dry for approximately 15 minutes. Do not
allow the mixture to impregnate that portion of the hairnet hanging above the top of a
clod.
NOTE: Alternately, the clod may be sprayed with water just prior to dipping in the
Saran:acetone solution. The water reduces the penetration of Saran into the
clod and produces a frost appearance, indicating the solution has coated the
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outside of the clod. Whichever alternative is chosen, it is important that the
same technique be used on all samples.
3. Apply additional dips as necessary until the clod does not produce excessive bubbles and
a coating of Saran is obtained that appears to be impervious to water. Usually three to
six dips is sufficient for most clods. Record the total number of dips made in the
laboratory under "LAB_DP", then re weigh the clod to the nearest 0.1 g and record this
weight under "LAB_WT". Also perform and record the dry-weight quality control check
(Section 5.5).
4. Add approximately 1600 ml of deionized water to a 2000-mL beaker. Place the beaker of
water on a balance and tare. Record the temperature of the water under "TEMP' so that
the density of the water can be calculated. Also perform and record the submerged
weight quality control check (Section 5.5).
5. Suspend the clod over the beaker by attaching the top of the hairnet to the test tube clip,
then lower the clod gently into the water until the top of the clod is entirely submerged.
Promptly, after three seconds, record the weight displayed on the balance to the nearest
0.1 g under "CLOD_H2O". If the clod floats, forcibly submerge it by pushing down with
forceps and record the weight. Note on the raw data form, with a "Y1 under "FLOAT1, that
the clod floated. Retare the balance before proceeding with other clods.
NOTE: When submerging, ensure that the clod is not touching the edge of the
beaker and that the clod label hangs freely. Occasionally, air bubbles may
rise from the clod and the weight reading on the balance does not stabilize
but steadily decreases. This occasionally occurs in clods sampled from
relatively porous surface horizons and simply indicates that all of the primary
macropores along the exterior of the clod were not thoroughly water-sealed.
By reading the weight immediately after submersion, error from this source
of instability is minimized. Note the bubbling on the raw data form under
"COMMENTS". Also note any other problem, such as a broken clod, under
"COMMENTS".
6. After submersion, place the clod in a pre-numbered evaporating dish and record the dish
number on the raw data form under "CRUC_NO". Remove as much of the clod label and
hairnet as possible and place in a large plastic bag with others from the same run.
7. Place the evaporating dish plus clod in a muffle furnace equilibrated at 400 *C. The
muffle furnace must be within an operating vented fume hood. Allow the Saran coating
to be burned off the clod surface for two hours. Allow the furnace to cool, then carefully
remove the evaporating dish from the muffle furnace. After the clod has cooled
thoroughly, place it in a pre-labeled, paper bag.
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8. Disaggregate the clod through a 2-mm sieve. Weigh any rock fragments retained on the
sieve to the nearest 0.01 g and record this weight under "R_FRAG". Place the rock
fragments into the paper bag and archive all such bags.
Alternatively, the clods may be soaked in water and dispersing agent to aid in
disaggregation. Wet sieving may be most efficient, followed by drying of coarse fragments at
105° C.
5.6.2 Known Volume Method
NOTE: Known volume bulk density samples are shipped from the field in small, plastic
bags. Upon passing the sample receipt verification, these samples can be placed
out to air dry in the drying area (see Section 4.6.1). The drying facilitates the
transfer of the entire sample from its plastic bag into a pre-labeled paper bag. Do
not remove any material from the bag, even if the material is thought to be
morphologically different from the type of horizon sampled.
NOTE: Record the set ID and sample code of the VR or VF sample on the known volume
bulk density raw data form (see Appendix B, Figure B-5).
1. Weigh the paper bag plus sample to the nearest 0.01 g and record this weight under
"AIR_WT".
2. Place the bag in a convection oven equilibrated at 105 *C for mineral soils and 60 *C for
organic soils. Allow the sample to oven dry overnight.
3. The following morning, remove the sample from the oven and allow to cool for 30
minutes. Weigh the sample to the nearest 0.01 g and record this weight under "OD_WT".
4. Sieve the contents of the bag through a 2-mm sieve to remove any rock fragments.
Weigh the rock fragments to the nearest 0.01 g and record this weight under "R_FRAG".
Place the rock fragments in the paper bag and archive all such bags.
5. Transcribe the computed volume (V, minus V,) for a VR sample from the sample receipt
log book to the "VOL" column on the raw data form. For a VF sample, 300 cm3 can be
automatically entered under "VOL".
5.7 Calculations
5.7.1 Clod Method
It is assumed that the weight of each two-second Saran coating applied in the field is equal
to the weight of each three-second coating applied in the laboratory, as some of the dipping
solution normally is absorbed into the clod when it is applied in the field.
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It is assumed that the specific gravity of air-dry Saran is 1.30 g/cm3 and that the coating loses
15 percent of its weight upon oven-drying. It is assumed that the particle density of the rock
fragments is 2.65 g/cm3.
It is assumed that the average gross weight of the hairnet and clod label is 1.88 g and the
net weight of the submerged portion of the hairnet is 0.20 g.
The following calculations may be performed by computer after the raw bulk density data are
entered. If so, it is advantageous to manually check a few samples using these calculations to
understand the procedure and to test the accuracy of the computer program. A list of temperature-
corrected water density values is provided in Table 5-1.
Table 5-1. Density of Pure Water*
Temp °C Water Density
13.0 0.9992
14.0 0.9991
15.0 0.9990
16.0 0.9988
17.0 0.9987
18.0 0.9986
19.0 0.9984
20.0 0.9982
21.0 0.9980
22.0 0.9978
23.0 0.9976
24.0 0.9973
25.0 0.9971
26.0 0.9968
27.0 0.9965
28.0 0.9963
29.0 0.9960
30.0 0.9957
31.0 0.9954
32.0 0.9951
33.0 0.9947
34.0 0.9944
35.0 0.9941
• Adapted from List (1984).
Use the following calculations to derive the weights and volume of the air-dry and oven-dry Saran
coatings:
SARAN WT [(FIELD_DP + LAB_DP) x (LAB_WT - FIELD_WT/DRY)]
19) LAB_DP
OD SARAN_WT (g) = SARAN_WT x 0.85
SARAN VOL (cm-) , SARA"-WT
V ' 1.30
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Use the following calculations to derive the volumes of rock fragments, water displacement, and
soil/pore fraction:
R FRAG
R_FRAG VOL (cm3)
WATER VOL (cm3)
2.47
CLOD H2O
DENSITY OF WATER
SOIL/PORES VOL (cm3) = WATER VOL - (R_FRAG VOL + SARAN VOL)
Finally, use the following calculation to derive the oven-dry bulk density (BD_CLD) for the individual
clod:
LAB WT - (R FRAG + OD SARAN WT + 1.88)
BD.CLD (g/cml - - SQl[/poRES VQL . „ ^
5.7.2 Known Volume Method
The particle density for rock fragments in a VR bulk density sample is derived individually by
a submersion technique similar to that used in the clod analysis. It is assumed that the particle
density for rock fragments in a VF bulk density sample is 2.65, unless specific particle density
measurments are made of different classes of rock fragment types.
The following calculations for known volume bulk density (BD_KV) may be performed by
computer. It is advantageous to manually check a few samples using these calculations to
understand the procedure and to test the computer program.
FINES_WT (g) = OD_WT - R_FRAG
FINES WT
BD_KV (g/cm3) =
5.8 References
VOL - (R_FRAG + particle density)
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specification for Reagent Water, D-1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
Blake, G. R. 1965. In Black, C. A (ed.) Methods of Soil Analysis, Part 1. American Society of
Agronomy, Madison, Wisconsin.
Flint, A. L., and S. Childs. 1984. Development and Calibration of an Irregular Hole Bulk Density
Sampler. Soil Science Society of America Journal 48 (2):374-378. Soil Science Society of
America, Madison, Wisconsin.
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Kern, J. S., and J. J. Lee. 1989. Evaluation of Two Alternative Bulk-Density Methods. Agronomy
Abstracts. American Society of Agronomy, Madison, Wisconsin.
Kern, J. S., M. L. Papp, J. J. Lee and L. J. Blume. In preparation. Appendix A In Kern, J. S. and J.
J. Lee, Direct/Delayed Response Project: Field Operations and the Mid-Appalachian Region of
the United States, U.S. Environmental Protection Agency, Office of Research and Development,
Washington, D.C.
USDA/SCS. 1984. Soil Survey Laboratory Methods and Procedures for Collecting Soil Samples. Soil
Survey Investigations Report No. 1. U.S. Government Printing Office, Washington, D.C.
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6.0 Field-Moist pH Determination
6.1 Overview
The pH is defined as the negative logarithm of the activity of hydrogen ions (H+). The H+
activity is a measure of the "effective" concentration of hydrogen ions in solution; it is always equal
to or less than the true concentration of hydrogen ions in solution. Values range from pH 1 to pH
14, with pH 1 most acidic, pH 7 neutral (at 25 *C), and pH 14 most alkaline. Each pH unit represents
a tenfold change in I-T activity (i.e., a pH 4 solution is 10 times as acidic as a pH 5 solution).
When the pH of a sample solution is measured, the hydrogen ions come into equilibrium with
the ion exchange surface (glass) of a calibrated pH electrode, which creates an electrical potential.
This voltage difference is measured by the pH meter in millivolts (mv), which is then converted and
displayed as pH units.
6.1.1 Scope and Application
This method is applicable to the determination of pH in soil samples. For the Direct/Delayed
Response Project (DDRP), field-moist pH is determined in the preparation laboratory using an Orion
Model 611 pH meter and an Orion Ross combination pH electrode. The method has been written
assuming that the Orion meter and electrode are used (Orion, 1983). The method, however, can be
modified for use with other instrumentation meeting specifications equivalent to those given in
Section 6.3.1.
The applicable pH range for soil solutions is 3.0 to 11.0.
6.1.2 Summary of Method
Immediately after a sample is spread to air dry, a field-moist subsample is collected and pH
in deionized water (DI) is determined. The pH can vary as much as one pH unit between the
supernatant and soil sediment. Always place the electrode junction at the same distance
(approximately 3 mm) above the surface of the soil sediment to maintain uniformity in pH readings.
6.1.3 Interferences
Factors that normally affect the measurement of pH are: (1) electrolyte content of the
extractant; (2) soil-to-solution ratio; (3) temperature and CO2 content of the extractant; (4) errors
that occur with instrument calibration, standard preparation, and liquid junction potential; (5) organic
and inorganic constituents; (6) length of time the soil and solution stand before they are measured;
and (7) technique used in reading the sample suspension.
Soils high in salts, especially sodium, may interfere with the pH reading and the electrode
response time. Clay particles may clog the liquid junction of the pH reference electrode junction,
slowing the electrode response time; thoroughly rinse the electrode with DI water between sample
readings to avoid this problem. Wiping the electrode dry with cloth, laboratory tissue, or similar
materials or removing the electrode from solution when the meter is not on standby may cause
electrode polarization.
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The initial pH of a nonalkaline soil will usually be as much as 0.5 pH unit greater than the pH
taken after the sample has set for 30 minutes or longer. The pH can vary as much as 1.0 pH unit
between the supernatant and soil sediment. Always place the electrode junction at the same
distance (approximately 3 mm) above the surface of the soil sediment to maintain uniformity in pH
readings.
6.1.4 Safety
Wear protective clothing (laboratory coat and gloves) and safety glasses when preparing
reagents, especially when concentrated acids and bases are used. The use of concentrated acids
should be restricted to a fume hood.
6.2 Sample Collection, Preservation, and Storage
The subsample used for determination of field-moist pH is taken from the bulk soil sample
immediately after it has been spread to air dry (see Section 4.6.1). The subsample is mixed with DI
water conforming to standards for ASTM Type I reagent grade water (ASTM, 1984). The sample is
stored at 4 *C prior to analysis.
6.3 Equipment and Supplies
6.3.1 Equipment Specifications
1. Digital pH/mV meter, capable of measuring pH to ±0.01 pH unit, potential to ±1 mV, and
temperature to ±0.5 *C. The meter must also have automatic temperature compensation
capability (Orion Model 611 or equivalent).
2. A combination pH electrode, made of high quality, low-sodium glass. At least two
electrodes (one as a backup) should be available. An Orion Ross combination pH
electrode or equivalent with a retractable sleeve is recommended. Do not use a Gel-type
reference electrode.
3. Balance, capable of weighing to 0.1 g
4. Balance calibration weights, 3-5 weights covering expected range.
6.3.2 Apparatus, Consumable Materials, and Reagents
1. National Bureau of Standards (NBS)-traceable thermometer.
2. Glass stirring rods.
3. 125-mL Nalgene bottles.
4. 25-mL and 50-mL plastic containers.
5. pH calibration buffers (pH 4.0 and 7.0)-Commercially available pH calibration buffers
(NBS-traceable) at pH values of 4.0 and 7.0 (two sets from different sources for
calibration and quality control checks).
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6. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
7. Potassium chloride (3 M)-Dissolve 224 g KCI in DI water and dilute to 1 L
8. Sodium hydroxide (NaOH) pellets.
9. Weighing pans, disposable.
10. Field-moist pH raw data form (Appendix B, Figure B-6).
11. Field-moist pH log book.
6.4 Calibration and Standardization
NOTE: For storage and readings, the electrode must be immersed to cover the liquid junction
of the reference electrode (typically about 3 cm). Rinse the electrode with DI water
between each sample and each buffer to prevent solution carryover. Do not rub or
blot the electrode dry because this may produce a static electric charge and polarize
the electrode.
6.4.1 Instrument Preparation
1. Plug in the instrument and verify that the control knob is on "STD BY." Allow at least 30
minutes for instrument warm-up prior to use.
NOTE: If instrument is used frequently, leave on and in "STD BY1 mode between uses.
2. Connect the combination electrode to the meter. Consult the pH electrode manual for the
proper procedure.
3. Verify that the level of reference filling solution (3 M KCI) in the electrode is just below the
fill hole and that the fill hole is uncovered during measurement (slide the plastic sleeve
down).
4. Calibrate the meter for temperature weekly using a two-point standardization (one point at
approximately 5 °C to 10 °C and the other point at room temperature).
a. Room temperature-Place the electrode and an NBS-traceable thermometer into DI
water which is at room temperature. Swirl the electrode for 5 to 10 seconds.
b. Turn the knob on the meter to "TEMP." Using a small screwdriver adjust the display,
using the "TEMP ADJ" screw on back of the pH meter, to the temperature reading of
the thermometer.
c. Cold temperature-Place the probe and the NBS-traceable thermometer into a 250-mL
beaker containing cold DI water (5 to 10 °C). Repeat Step b by adjusting the display
with the "TEMP SLOPE" screw on the back of the meter.
d. Continue steps a through c until no further adjustments are necessary and record all
values in the logbook.
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6.4.2 Calibration with Buffers
1. Check the meter temperature calibration daily with a beaker of room temperature, 01 water
and an NBS-traceable thermometer. If the display differs from the NBS-traceable
thermometer by more than 1.0 °C, complete adjustments as described in Section 6.4.1,
above.
2. Pour fresh pH 7.00 and pH 4.00 buffer solutions into labeled 50-mL beakers (one "RINSE",
one "CALIBRATION," and one "CHECK" beaker for each buffer). Rinse all beakers three
times and fill with the appropriate buffer solutions.
3. Rinse the electrode with DI water. Place the electrode into the pH 7.00 "RINSE" beaker and
swirl for 40 seconds. Place the electrode into the "CALIBRATION" beaker, turn the knob to
"pH", swirl for 30 to 60 seconds (or until the pH reading is stable), and read the value on the
display. Consult the pH-temperature chart, Table 6-1. Use the "CALIBRATE" knob to adjust
the pH reading on the meter to the theoretical pH of the buffer solution at the appropriate
temperature.
4. Repeat Step 3 for pH 4.00 buffer using the "% SLOPE" knob to adjust the pH reading.
5. Repeat steps 3 and 4 until both the pH 7.00 and the pH 4.00 buffers agree with the
theoretical pH of the buffer solution at the appropriate temperature.
6. Check the standardization using the buffer solutions in the "CHECK" beakers. If the values
differ by more than ±0.03 units from the theoretical value, repeat the standardization
process. When the meter standardization is acceptable, record the pH and temperature
readings for each buffer solution in the pH logbook.
Table 6-1. pH Values of Buffers at Various Temperatures
Temperature
25 °C
1.68
3.78
4.01
6.86
7.00
7.41
9.18
10.01
0 °C
1.67
3.86
4.00
6.98
7.11
7.53
9.46
10.32
5 °C
1.67
3.84
4.00
6.95
7.08
7.50
9.40
10.25
10 °C
1.67
3.82
4.00
6.92
7.06
7.47
9.33
10.18
20 °C
1.67
3.79
4.00
6.87
7.01
7.43
9.23
10.06
30 °C
1.68
3.77
4.02
6.85
6.98
7.40
9.14
9.97
40 °C
1.69
3.75
4.03
6.84
6.97
7.38
9.07
9.89
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6.4.3 Maintenance
1. Weekly, drain the 3 M KCI filling solution from the electrode using a disposable pipet with
Teflon tubing attached.
2. Refill the electrode chamber with the 3 M KCI filling solution and rinse by inverting the
electrode. Drain the solution as in Step 1.
3. Refill the electrode with the filling solution to just below the fill hole.
4. Gently spin the electrode overhead for approximately 1 minute by the leader to remove any
air bubbles. Be careful to stand clear of any obstacles when swinging the electrode.
6.4.4 pH Meter Electronic Checkout
NOTE: This procedure should be performed whenever a new pH meter is set up or when
calibration problems occur.
1. Connect the shorting strap as outlined in the Orion pH meter manual.
2. Turn the "TEMP ADJ" and "TEMP SLOPE1 screws fully counterclockwise and record the
display pH value (turn knob to "pH" position).
3. Turn the "TEMP SLOPE" screw 7.5 turns clockwise and record the display pH value. The
difference between the "TEMP SLOPE" value in Step 2 and Step 3 should be between 7.0 and
15.0.
4. Turn the "TEMP ADJ1 screw until a value between 50.0 t 0.1 appears on display.
5. Press the test button. A value of 42.2 t 2.0 should appear on the display when the knob
is in the "TEMP1 position. If this value is not displayed, keep depressing the test button and
use the "TEMP SLOPE" screw to adjust the reading to 4.0 ± 1.0. Release the test button and
use the "TEMP ADJ1 screw to obtain a reading of 50.0 ± 0.1. Press the test button again.
The reading should be 42.2 ± 2.0. Repeat this procedure several times if the value is not
in range.
6.4.5 Electrode Etching Procedure
NOTE 1: Use extreme caution when using the NaOH pellets. Be sure to wear gloves, eye
protection, and a rubber apron.
NOTE 2: If the electrode response is sluggish or if the instrument cannot be standardized,
the following procedure is recommended for cleaning the ceramic junction of the
electrode and improving the electrode response time.
NOTE 3: Etch electrodes in groups of three when possible. Prepare a fresh NaOH solution
for each group of electrodes.
1. Drain the filling solution from the electrode.
2. Rinse the filling chamber with DI water and drain it.
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3. Refill the chamber with DI water.
4. Prepare a 50 percent (w/v) NaOH solution by slowly adding 30 g of NaOH to 30 ml_ of DI
water.
5. Gently stir the solution with up to three electrodes to dissolve the NaOH. The solution will
be very hot and may boil and splatter; caution must be used.
6. Stir the solution an additional 2 minutes with the electrodes.
7. Rinse the electrodes with DI water.
8. Rinse the electrodes in pH 7.00 buffer for 2 minutes.
9. Drain the DI water from the filling chambers.
10. Refill each electrode with 3 M KCI, agitate the electrodes, and drain the chambers.
11. Refill the chambers once more with 3 M KCI and spin each electrode from the leader to
remove air bubbles.
6.5 Quality Control
6.5.1 Initial Quality Control Check
1. Rinse and fill two beakers with pH 4.00 quality control (QC) solution. Use a different batch
of traceable stock buffer solution than that used for calibration.
2. Rinse the electrode by swirling it in the rinse beaker for 15 to 30 seconds.
3. Insert the electrode into the measurement beaker.
4. Turn the knob to "pH". Wait until the reading seems fairly consistent, then note the time and
pH values on a loose sheet of paper. If the pH reading does not vary by more than 0.02
pH units in one direction after a 1-minute interval, the reading is considered stable. Record
the stable pH and temperature readings in the logbook.
6.5.2 Routine Quality Control Checks
NOTE: The pH 4.00 QC solution is analyzed at the beginning of a batch and at the end of a
batch. The quality control check sample (QCCS) also is analyzed at intervals within
the batch as specified by the quality assurance program.
1. Measure and record the QC solution by following the instructions in Section 6.5.1.
2. If the measured QC solution pH is acceptable (pH 4.00 ±0.05), proceed with routine sample
pH determinations.
3. If the QC solution pH is not acceptable, follow the steps below until an acceptable value
is obtained:
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a. Repour the pH 4.00 QC solution into a beaker and reanalyze.
b. Clean the reference junction of the electrode.
c. Check that the wiring straps into the meter are firmly connected and perform the
electronic check as described in Section 6.4.4.
4. If the pH meter requires recalibration to obtain an acceptable QC reading, make a notation
in the pH logbook. Determine which samples should be reanalyzed. Reanalyze all samples
back to the last acceptable QC check.
6.5.3 Quality Control/Quality Evaluation Samples
Rep//cafes~Jen percent of the samples in each batch should be analyzed in duplicate. The
difference should be 0.15 pH units or less.
QC Audit Sample (QCASj-The QCAS should fall within the accuracy window provided by the
QA manager.
NOTE: Because the pH is measured immediately after a sample is spread to air dry, the
number of samples in each run varies. It is necessary to adhere to all calibration
protocols and QC specifications for all runs, regardless of size.
6.6 Procedure
6.6.1 Sample Preparation
1. After spreading and stirring the field-moist soil, scoop approximately 50 g of mineral soil
or 15 g of organic soil into a 125-mL Nalgene bottle and record the sample code on the
label of the bottle. Refrigerate the bottles at 4 *C until the analyst is ready to begin a
run.
NOTE: Some soils may be in a saturated state when received. Follow the
procedure as stated; however, note the saturated condition of the soil on the
bulk sample processing raw data form.
2. Place approximately 20 g of mineral soil or 5 g of organic soil into a pre-numbered 25-mL
plastic container. Add 20 mL of DI water for mineral soils, or 25 ml_ for organic soils.
Record the sample code and the container number on the field-moist pH raw data form.
3. Allow the sample to absorb the solution for approximately 60 seconds, then thoroughly
stir the soil-solution mixture for 10 seconds with a glass stirring rod. Rinse the rod with
DI water after stirring each sample. Stir again for 10 seconds after 15, 30, 45, and 60
minutes. Allow the suspension to settle for 30 minutes.
6.6.2 Sample Measurement
1. Place the pH electrode in the supernatant of the soil suspension. For mineral soils, the
electrode junction is to be below the solution surface and above the soil-solution
interface. Although organic soils normally absorb all of the free water available, an
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acceptable reading generally is obtained if the electrode junction is below the meniscus
of the organic material.
2. Record the pH of each sample (PH_MP) on the field-moist pH raw data form. Transcribe
the pH values onto the appropriate entry field of each bulk sample processing raw data
form (Appendix B, Figure B-3).
3. After the pH measurements are completed, store the electrode in storage solution. Do
not allow the sensing element or reference junction to dry out. The level of the storage
solution should be one inch below the filling solution level. The electrode sleeve is to be
closed during storage. Check periodically to ensure that the electrode reservoir is full of
storage solution.
6.6.3 Cleanup
1. Copiously rinse the electrode and glassware with DI water.
2. Cover the fill hole of the electrode with the plastic sleeve and store the electrode in 3 M
KCI.
3. Make sure the meter is on "STD BY".
6.7 Calculations
No calculations are required to obtain pH values. Replicate measurements of the same
sample or of duplicate samples should not be averaged.
6.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specification for Reagent Water, D 1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
Orion Research Incorporated. 1983. Instruction Manual - Model 611 pH/millivolt meter. Orion,
Cambridge, Massachusetts.
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7.0 Organic Matter Determination by Loss-On-Ignition
7.1 Overview
Loss-on-ignition (LOI) is the method used to determine an approximation of percent organic
matter of soil samples. Because organic samples are oxidized at high temperatures, percent
organic matter can be calculated on a weight-loss basis. From the percent organic matter, the
percent organic carbon can be estimated. In the DDRP, LOI was used to classify samples as
mineral or organic for subsequent analysis purposes. Organic material has between 12 and 18
percent organic carbon depending on the clay content of the mineral material (USDA/SCS, 1975).
A 20 percent LOI was selected as the definition point, which corresponds to approximately 12
percent organic carbon.
7.1.1 Summary of Method
Oven-dried soil samples are ashed in a muffle furnace to remove organic material. The
difference in pre- and post-ashing weights is used to calculate percent organic content. A modified
version of the method described in MacDonald (1977) is used.
7.1.2 Interferences
Crucibles must be thoroughly cleaned after each use, as the crucible weights are pre-
determined and used in the calculation of results. Tongs or finger cots should be used when
transferring crucibles from one location to another.
Caution should be used when interpreting the results of low organic content soil. In addition
to organic matter, structural water and some soluble salts are commonly lost when heated to
450 °C.
7.1.3 Safety
Laboratory personnel should use caution when working around the muffle furnace, as
temperatures of up to 450 *C are common. The furnace should be activated only in an operable
fume hood. Heat resistant gloves may be needed when placing samples in the furnace. The
furnace must be adequately vented and protected from human contact and combustible materials.
7.2 Sample Collection, Preservation, and Storage
A subsample is taken from the bulk soil sample after it has been spread to air dry (see
Section 4.6.1). Samples may be stored at 4 *C until ready for analysis.
7.3 Equipment and Supplies
7.3.1 Apparatus
1. Balance, capable of weighing to 0.01 g.
2. Small crucibles, pre-numbered.
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3. Tongs.
4. Desiccator, with desiccant and crucible plate.
5. Muffle furnace in operating fume hood.
6. Convection oven.
7. Balance calibration weights, 3-5 weights covering expected range.
7.3.2 Consumable Materials
1. Finger cots.
2. Furnace gloves.
3. Loss-on-ignition raw data forms (Appendix B, Figure B-7).
4. Loss-on-ignition log book.
7.4 Calibration and Standardization
Calibration of the balance is detailed in Appendix A, General Laboratory Procedures.
7.5 Quality Control
NOTE: Refer to Section 3.2 for additional information concerning these internal quality control
(QC) checks.
Replicates-Qne sample from each batch should be analyzed in duplicate. The percent relative
standard deviation (%RSD) should be 15 percent or less.
QC Audit Sample (QCAS)~~ft\e QCAS should fall within the accuracy window provided by the
quality assurance (QA) manager.
7.6 Procedure
NOTE: The LOI analysis can be performed at any time while the samples are air drying. The
data obtained are to be recorded on the loss-on-ignition raw data form (see Appendix
B, Figure B-7).
1. Fill a small pre-numbered and pre-weighed crucible about two-thirds full of soil. Record
the sample code and crucible number on the raw data form under "CRUCJMO". Oven dry
the crucible plus sample overnight at 105 *C for mineral samples or 60 *C for organic
samples.
2. The following morning, remove the crucible from the convection oven and place it in a
desiccator for 30 minutes. Weigh the crucible plus sample and record its oven-dry weight
under "OD WT."
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3. Carefully place the crucible plus sample in a muffle furnace and secure the door. Set the
furnace temperature at 450 *C and turn on the unit. The sample should be left overnight
at this temperature.
4. The following morning, turn the furnace off and allow to cool for 30 minutes. Carefully
remove the crucible from the furnace and allow to cool in the desiccator with a dish of
desiccant.
NOTE: Because a vacuum may be created when cooling extremely hot samples,
extra caution should be exercised when opening the desiccator. If a vacuum
has formed, the lid may be extremely hard to remove and/or a rush of air
may enter the desiccator upon opening.
5. Weigh the crucible plus remaining soil and record this weight under "ASHED_WT" on the
raw data form.
7.7 Calculations
The following calculation may be performed by computer after the raw data are entered. It
is advantageous to manually check a few samples using the calculation to understand the
procedure and to test the accuracy of the computer program.
OD WT - ASHED WT
Percent Organic Matter (OMJ.OI) = QD"WT _ CRUC WT x 10°
If the calculated organic matter content is 20 percent or more, the sample is assumed to be
an organic sample. If any samples which were initially labeled as mineral are determined to have
20 percent or more organic matter, batch these with the organic samples, or vice versa. Report
these samples to the QA manager and the soil sampling task leader as soon as possible.
7.8 References
MacDonald, C. C. 1977. Methods of Soil and Tissue Analysis in the Analytical Laboratory. Maritimes
Forest Research Centre Information Report, M-X-78. Fredericton, New Brunswick, Canada.
U.S. Department of Agriculture/Soil Conservation Service. 1975. Soil Taxonomy: A Basic System
of Soil Classification for Making and Interpreting Soil Survey. Agriculture Handbook No. 436,
U.S. Department of Agriculture, U.S. Government Printing Office, Washington, D.C. 754 pp.
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8.0 Air-Dry Moisture Determination
8.1 Overview
Air-dry moisture determination is done both at the preparation laboratory and at the analytical
laboratory. The procedure for assessing air-dry moisture is not to be performed, however, until the
soil is believed to be air dry (see Section 4.6.1). In the preparation laboratory, the process is used
to ensure that each sample is at an acceptable moisture level for further processing. In the
analytical laboratory, the air-dry moisture is determined on all samples to convert all results to an
oven-dry basis, and if specified in a procedure, to calculate the weight of sample equivalent to a
given weight of oven-dry soil (Brady, 1974).
8.1.1 Summary of Method
A subsample of the air-dried bulk soil sample is weighed, oven-dried for approximately 24
hours, and reweighed. The initial and final weights are used to calculate a percent weight loss.
8.1.2 Interferences
Sample weights can be affected by salts, oils, and moisture present on skin. Losses of fine
silt and clay, caused by excessive movement of the samples, will cause erroneously calculated
moisture values.
8.1.3 Safety
Forceps or heat-resistant gloves should be used to handle weighing dishes after removal from
the oven.
8.2 Sample Collection, Preservation, and Storage
A subsample is taken from the bulk soil sample after it is believed to be fully air-dried.
Analysis takes places immediately thereafter; no preservation or storage is required.
8.3 Equipment and Supplies
8.3.1 Apparatus
1. Balance, capable of weighing to 0.01 g.
2. Convection oven.
3. Desiccator and desiccant.
4. Forceps or finger cots.
5. Thermometer, 0 °C to 200 °C range.
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6. Weighing containers capable of withstanding intermittent heating to 110 °C and cooling
to room temperature (analytical laboratory).
7. Balance calibration weights, 3-5 weights covering expected range.
8.3.2 Consumable Materials
1. Aluminum weighing dishes, pre-numbered (preparation laboratory).
2. Aluminum weighing pans, disposable (analytical laboratory).
3. Gloves, unpowdered.
4. Air-dry moisture raw data forms (Appendix B, Figure B-8) (preparation laboratory) and air-
dry moisture log book (analytical laboratory).
5. Form 1, air-dry moisture percent, and Form QC-1 (Appendix B, figures B-9 and B-10,
respectively).
8.4 Calibration and Standardization
The calibration of the balance is described in Appendix A, General Laboratory Procedures. The
thermometers should be checked periodically to ensure that they are measuring temperature
accurately. The oven should be monitored to ensure that temperature fluctuation does not exceed
±5°C.
8.5 Quality Control
NOTE: Analytical laboratory quality control (QC) results are recorded on Form QC-1 (Appendix
B, Figure B-10). Refer to Section 3.2 for additional information concerning these
internal QC checks.
fiep//cates~Or\e sample from each batch should be analyzed in duplicate. The percent relative
standard deviation (%RSD) should be 15 percent or less.
QC Audit Sample (QCAS)~~ft\e QCAS should fall within the accuracy window provided by the
quality assurance (QA) manager.
8.6 Procedure
8.6.1 Preparation Laboratory
NOTE: Data for this procedure are recorded on the air-dry moisture raw data form (see
Appendix B, Figure B-8). Once a soil sample is determined to be air dry, the
information is also entered on the bulk sample processing raw data form
(Appendix B, Figure B-3).
1. Thoroughly mix the air-dry sample with gloved hands. Transfer a subsample of
approximately 15 g into a pre-numbered aluminum weighing dish of known weight. Enter
the dish number on the air-dry moisture raw data form under "TIN_NO." Handle the
weighing dish with forceps or finger cots.
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NOTE: Because the aluminum weighing dishes are manufactured to be a nearly-
constant weight, the average weight of ten labeled aluminum weighing
dishes may be used.
2. Weigh the dish plus sample to the nearest 0.01 g and record this initial weight under
"INIT_WT." Place the dish in a convection oven which has equilibrated at 105 *C for
mineral samples or 60 *C for organic samples. Allow the sample to oven dry overnight
at this temperature.
3. The following morning, remove the sample from the oven and allow to cool for 30 minutes
in a desiccator. Weigh the dish plus sample to the nearest 0.01 g and record this oven-
dry weight under "OD_WT."
8.6.2 Analytical Laboratory
NOTE: Data for this procedure are recorded on Form 1 oven dried moisture percent
(Appendix B, Figure B-9). Figures within the square brackets, [ ], represent the
form number and column in which the data are recorded.
1. Allow oven to equilibrate at the required temperature ±5 °C for at least 24 hours. Heat
the oven to 105 °C for mineral soils; 60 °C for organic soils.
2. Tare each weighing pan to the nearest 0.01 g and note this value for future calculations.
3. Weigh 10.00 g of mineral soil or 6.00 g of organic soil and record the exact air-dry weight
[1-B].
4. Dry soils for 24 hours.
5. Remove weighing pan from oven; allow soil to cool in a desiccator. Weight each sample
to ±0.01 g and record oven-dry weight [1-CJ.
8.7 Calculations
8.7.1 Preparation Laboratory
The following calculations may be performed by computer. It is advantageous to manually
check a few samples using these calculations to understand the procedure and to test the accuracy
of the computer program.
INIT WT - OD WT
Percent air-dry moisture (MOIST_P) = ~ •— ~ x 100
If the calculated moisture content is above 2.5 percent for mineral soils or above 6.0 percent
for organic soils, allow the bulk sample to continue air-drying and repeat the procedure at a later
time. However, if the sample is below the cutoff percent moisture content for the soil type, then the
air-dry sample may be rebagged and placed in cold storage or it may immediately undergo the next
stage of processing.
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A 7.2 Analytical Laboratory
NOTE: Designations within the square brackets, [ ], represent the form number and column
in which the data are recorded on Form 1 (Appendix B, Figure B-9).
Percent moisture = ([Air-dry wt. - Oven-dry wt.] + Oven-dry wt.) x 100
MOIST [1-D] = ([1-B] - [1-C]) + [1-C] x 100
8.8 References
Brady, N.C. (ed.). 1974. The Nature and Property of Soils. Eighth Edition. MacMillan
Publishing Co., Inc., New York, New York.
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9.0 Particle Size Analysis
9.1 Overview
Particle size analysis is determined on the less than 2-mm fraction from mineral horizons only.
The sieve/pipet/gravimetric method described in Soil Survey Laboratory Methods and Procedures for
Collecting Soil Samples (USDA/SCS, 1984) is used.
9.1.1 Summary of Method
Organic matter is removed from the sample by digestion with hydrogen peroxide. The sand
fractions are separated from the silt and clay fractions by wet sieving. The silt and clay fractions
are suspended in water; aliquots taken from the suspension under specified conditions are dried
and then weighed. The sand fractions are sieved and each fraction is weighed. The resulting
gravimetric data allow calculation of the percentage of each particle size class.
9.1.2 Interferences
While the soil in suspension is settling, the graduated cylinders containing the suspension
cannot be disturbed, nor can the temperature vary. Foam insulation, a constant temperature water
bath, or temperature-controlled room may be used to maintain constant temperature. When
handling weighing bottles, use forceps, finger cots, cotton gloves, or vinyl gloves to avoid adding
weight from moisture and from body salts and oils.
9.1.3 Safety
Forceps or heat-resistant gloves should be used to handle weighing bottles after removal from
the oven. Use waterproof gloves while handling hydrogen peroxide. Wear protective clothing and
safety glasses when handling reagents or operating instruments.
9.2 Sample Collection, Preservation, and Storage
The subsamples for particle size analysis are taken from the bulk soil sample after it has been
air dried, homogenized, and tested for moisture content (see sections 4.0 and 8.0). Samples should
be stored at 4 *C until ready for analysis.
9.3 Equipment and Supplies
9.3.1 Apparatus
1. Fleaker, Erlenmeyer flask, or other suitable container, 250-mL or equivalent (tare to ±0.1
mg).
2. Pasteur-Chamberlain filter candles (or equivalent), fineness "F"; store in double-deionized
water.
3. Reciprocating shaker, 120 oscillations per minute.
4. Sedimentation cylinders (1-L graduated cylinders, optional).
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5. Stirrer, motor-driven.
6. Stirrer, hand-Fasten a circular piece of perforated plastic to one end of a brass rod.
7. Shaw pipet rack or equivalent.
8. Pipets, 25-mL, automatic (Lowry with overflow bulb or equivalent).
9. Polyurethane foam pipe-insulation, constant temperature bath (±1 *C), or temperature-
controlled room (±1 *C).
10. Sieve shaker, 1.25-cm vertical and lateral movement, and 500 oscillations per minute, or
equivalent. Unit must accommodate a nest of sieves.
11. Glass weighing bottles, 90-mL, wide-mouth with screw caps, or equivalent, (tare to ±0.1
mg), capable of withstanding intermittent heating to 110 *C and cooling to room
temperature.
12. Balance, top-loading, capable of weighing to 0.01 g.
13. Balance, analytical, capable of weighing to 0.0001 g.
14. Set of sieves, square-mesh, woven phosphor-bronze or stainless steel wire cloth; U.S.
Series and Tyler Screen Scale equivalent designations as follows:
Nominal
Openina (mm)
1.0
0.5
0.25
0.105
0.046
U.S.
No.
18
35
60
140
300
Tyler
Mesh Size
16
32
60
150
300
15. Receiving pan, used with sieves.
16. Hot plate (block digester, optional).
17. Thermometer, range 10 to 50 *C.
18. Evaporating dishes, or equivalent, 125- or 250-mL
19. Desiccator and desiccant.
20. Watch glass.
21. Convection oven.
22. Clamp and ring stand.
23. Stoppers (optional).
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24. Stop watch.
9.3.2 Reagents and Consumable Materials
1. Hydrogen peroxide (H2O2), 30 to 35 percent.
2. Sodium carbonate (Na2CO.j).
3. Sodium hexametaphosphate [(NaPOJJ, dispersing agent-Dissolve 35.7 grams of (N
and 7.94 grams of Na2CO3 in deionized (DI) water and dilute to 1 L
4. Phosphorus pentoxide (P20^~Used as desiccant.
5. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
6. Kimwipes.
7. Forms-Form 2 particle size parameters raw data, Form 3 particle size parameters
calculated data, Form QC-2, and Form QC-3 (Appendix B, figures B-11 through B-14,
respectively).
9.4 Calibration and Standardization
Periodically check thermometers against an NBS-certified standard to ensure that they are
measuring temperature accurately. Temperatures of the suspensions should vary no more than
±1 °C.
Calibration of the balance is described in Appendix A, General Laboratory Procedures.
9.5 Quality Control
NOTE: Log all QC data on Forms QC-2 and QC-3 (Appendix B, figures B-13 and B-14); refer
to Section 3.2 for additional information concerning these internal QC checks.
Reagent Blanks-k 25-mL aliquot of the diluted dispersion solution (10.0 mL of the
hexametaphosphate dispersion solution diluted to 1 L), dried and weighed, is used as the clay
reagent blank. One blank should be analyzed with each batch.
f?ep//c3fas-One sample from each batch should be analyzed in duplicate. The percent relative
standard deviation (% BSD) should meet the limits in Table 3-1.
Quality Control Check Standard (QCCS) - A well-characterized soil having a minimum of 5
percent each of sand, silt, and clay is analyzed with each batch of soils. This QCCS standard is
analyzed at least once with each group of soils. For example, if the analytical laboratory has eight
sets of sedimentation cylinders-stirrers-pipets, one of these sets would be used for the QCCS
sample with every seven or fewer soil samples. Although data for all fractions are reported on Form
QC-2 and QC-3, only the to/a/sand, silt, and clay fractions are subjected to the criterion that the
percent relative standard deviation (%RSD) between measured and known values is 10 percent or
less.
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QC Audit Sample (QCASJ-The QCAS should fall within the accuracy window provided by the
quality assurance (QA) manager.
9.6 Procedure
NOTE: Figures within the square brackets, [ ], represent the form number and column in
which the data are entered on forms 2 and 3, particle size parameters, raw data and
calculated data, respectively (Appendix B, figures B-11 and B-12).
9.6.1 Removing Organic Matter
1. Weigh 10.00 g air-dried soil into a tared (to the nearest 0.01 g) Fleaker or equivalent and
record this value [2-B]. For soils low in clay, it may be necessary to double the amount
of soil to meet the required precision. Doubling the amount of soil does not require any
adjustments to the remaining steps in this procedure.
2. Add 50 mL of DI water followed by 5 mL of H2O2. Cover the Fleaker with a watch glass
to avoid sample loss. If a violent reaction occurs, repeat the H2O2 treatment periodically
until no more foaming occurs.
NOTE: If foaming results in sample loss, repeat from Step 1.
3. Heat the Fleaker to about 90 *C on an electric hot plate. Add H2O2 in 5-mL quantities at
45-minute intervals until the organic matter is destroyed, as determined visually by a lack
of effervescence. Continue heating for about 30 minutes to remove excess H2O2.
NOTE: For simplicity, use block digestion apparatus, if available, and replace Fleakers with block
digester tubes. The removal of the organic matter may require 24 to 36 hours.
4. Place the Fleaker in a rack and add about 150 mL of DI water in a jet strong enough to
stir the sample well. Remove solution from the suspension with a filter-candle system.
Five such washings and filterings are usually sufficient; soils containing much coarse
gypsum may require additional treatments.
5. Remove soil that adheres to the filter by applying gentle air pressure.
6. Dry the sample overnight in an oven at 105 *C, cool the sample in a desiccator, and weigh
the H2O2-treated sample plus Fleaker to the nearest 0.01 g and record the soil weight [2-
C]. Use the weight of the oven-dry, H2O2-treated sample as the weight for calculating
percentages of the particle-size fractions.
9.6.2 Separating Sand from Silt and Clay
1. Add 10 mL of sodium hexametaphosphate dispersing agent (see Section 9.3.2, Step 3) to
the Fleaker that contains the oven-dry treated sample. Bring the volume to approximately
200 mL. Stopper the Fleaker and shake overnight on a horizontal reciprocating shaker at
120 oscillations per minute.
2. Place a 300-mesh sieve on top of the sedimentation cylinder. A clamp and ring stand may
be used to hold the sieve in place. Wash the dispersed sample onto the sieve with DI
water. Avoid using jets of water because they may break the fine mesh of the sieve.
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Fine silt and clay will pass through the sieve into the cylinder. The sand and some coarse
silt will remain on the sieve. It is important to wash all particles of less than 0.02-mm
diameter through the sieve. Gently tapping the sieve clamp with the side of the hand will
facilitate sieving.
3. Continue washing the sand until the suspension volume in the cylinder is about 800 ml.
4. Remove the sieve from the cylinder. Wash the sand into a tared evaporating dish or
original Fleaker with DI water. Dry the sand overnight at 105 *C. Continue to Section
9.6.3 for fractionation of the sand.
5. Dilute the silt and clay suspension in the cylinder to 1.00 L with DI water. Cover the
cylinder with a watch glass. Continue to Section 9.6.4 for the separation of the fine silt
and clay.
9.6.3 Sieving and Weighing the Sand Fractions
1. Weigh the total dry sand (from 9.6.2, Step 4) to the nearest 0.01 g and record [2-D].
2. Stack sieves (tared to the nearest 0.01 g) from largest opening (1.0 mm) to smallest
nominal opening with the 1.0 mm sieve on the top and the receiving pan on the bottom.
3. Quantitatively transfer the dried sand to the top sieve.
4. Cover and secure the stack of sieves and shake for 3 minutes.
5. Weigh the sand fraction retained by each sieve to nearest 0.01 g and record; [2-E] very
. coarse; [2-F] coarse, [2-G] medium; [2-H] fine; [2-1] very fine.
9.6.4 Pipetting
All pipetting must be performed in a location free from drafts and temperature fluctuations.
A temperature-controlled room, constant-temperature water bath, or foam insulation may be used.
1. Allow 12 to 24 hours for the temperature of suspension to equilibrate.
2. Stir the material in the sedimentation cylinder for 6 minutes with the motor-driven stirrer.
Stir 8 minutes if suspension has been standing for more than 16 hours.
If stoppers of adequate size are available, it is preferable to stopper the cylinder, invert,
and swirl. Care must be taken to ensure that the stopper is held tightly in the cylinder.
Repeat this procedure at least six times. Inspect the bottom and sides of the cylinder
to ensure that fine particles are not adhering to the glass walls of the cylinder.
3. Remove the stirrer and either (1) cover the cylinder with a length of polyurethane foam
pipe-insulation, (2) immerse the cylinder in a constant-temperature water bath, or (3) place
the cylinder in a temperature-controlled room.
4. Stir the suspension for 30 seconds with a hand stirrer; use an up-and-down motion.
Record the time when the stirring is complete. Do not move, stir, or otherwise disturb the
cylinder from this point until all pipetting has been completed.
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5. Take the temperature of the solution in the cylinder by gently lowering a thermometer 5
cm into the suspension. Support the thermometer with a clamp to reduce disturbance
to the suspension.
6. Use the temperature and Table 9-1 to determine the settling time required for the <0.02-
mm fraction, e.g., at 22 *C allow 4 minutes, 35 seconds.
Table 9-1. Sedimentation Times for Fin* Silt and Clay Particle* Settling Through Water to a Depth of Ten
Centimeters
Settling Time with Indicated Particle Diameter*
Temperature
°C
20
21
22
23
24
25
26
27
28
29
30
31
<0.002 mm
hrmin
8:00
7:49
7:38
7:27
7:17
7:07
6:57
6:48
6:39
6:31
6:22
6:14
<0.02 mm
mirrsec
4:48
4:41
4:35
4:28
4:22
4:16
4:10
4:04
4:00
3:55
3:49
3:44
"Values calculated from Stokes' equations, assuming a particle density of 2.65 g/cm3. This figure for particle density is
arbitrary and has been chosen to satisfy simultaneously the two definitions of the clay fraction, i.e., particles that have
an effective diameter of 0.002 mm or less and particles that have a settling velocity of 10 cm in 8 hours at 20 °C.
7. Approximately 60 seconds before the sedimentation time has elapsed, slowly lower the
Lowry automatic pipet 10 cm into the suspension. (A 25-mL volumetric pipet premarked for
a 10-cm depth and clamped firmly in place on a stand may be used.)
8. At the appropriate time, slowly (allow about 12 seconds) fill the pipet. Carefully remove it
from the suspension.
9. Wipe clean the outside of the pipet and empty the contents into a drying container, such
as a 90-mL widemouth bottle, tared to the nearest 0.1 mg. Rinse the pipet into the bottle
once with DI water (add the rinse water to the contents of the bottle).
10. Dry the bottle and contents in an oven overnight at 105 *C. Cool in a desiccator over
phosphorus pentoxide (P2O^. Weigh to nearest 0.1 mg and record net weight [2-J] to
nearest 0.1 mg.
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11. Repeat steps 5 through 10 for the <0.002-mm clay fraction. The <0.002-mm fraction may
be pipetted at a time between 5 and 8 hours depending on the temperature and the table
used. The use of Table 9-1 and a depth of 10 cm is strongly recommended and is the
easiest method. Table 9-2 should be used only when time constraints necessitate. Weigh
dried material and record net weight [2-K] to nearest 0.1 mg.
Table 9-2. Sedimentation Tlmet and Pipetting Depth* for Clay Particle*
Sedimentation Time*
Temperature °C 5 hr. 5 hr. 30 min. 6 hr. 6 hr. 30 min.
20.0
20.5
21.0
21.5
22.0
22.5
23.0
23.5
24.0
24.5
25.0
25.5
26.0
26.5
27.0
27.5
28.0
28.5
29.0
29.5
30.0
6.44
6.52
6.59
6.68
6.75
6.88
6.91
6.98
7.08
7.15
7.24
7.31
7.40
7.47
7.56
7.64
7.74
7.82
7.91
7.99
8.08
"~~"— r I}JQIUII^ isvpui \\
7.08
7.17
7.25
7.34
7.43
7.54
7.60
7.69
7.78
7.86
7.96
8.05
. 8.14
8.22
8.32
8.40
8.51
8.61
8.70
8.79
8.88
f\ I \f —
7.72
7.82
7.91
8.01
8.11
8.21
8.30
8.39
8.49
8.59
8.69
8.78
8.88
8.97
9.08
9.17
9.28
9.39
9.49
9.59
9.69
8.37
8.47
8.57
8.68
8.78
8.88
8.98
9.09
9.20
9.30
9.41
9.51
9.62
9.72
9.83
9.93
10.06
10.17
10.28
10.39
10.50
"Calculations provided by USDA/SCS National Soil Survey Laboratory, Lincoln, Nebraska (personal
communication) (assuming a particle density of 2.65 g/cm ).
9.7 Calculations
NOTE: Designations within the square brackets, [ ], represent the form number and column
in which the data are entered on forms 2 and 3, particle size parameters, raw data
and calculated data, respectively (Appendix B, figures B-11 and B-12).
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9.7.1 Input (raw data)
[2-B] = air-dry sample weight
[2-C] = treated (oven-dry, organic-free) sample weight
[2-D] = oven-dry net weight of total sand
[2-E] = oven-dry net weight of very coarse sand
[2-F] = oven-dry net weight of coarse sand
[2-G] = oven-dry net weight of medium sand
[2-H] = oven-dry net weight of fine sand
[2-1] = oven-dry net weight of very fine sand
[2-J] = oven-dry net weight of first pipet
[2-K] = oven-dry net weight of second pipet
RBLK1 = weight of clay reagent blank
9.7.2 Calculated Data
All calculations are made to the nearest 0.1 weight percent.
SAND [3-B] = ([2-E] + [2-F] + [2-G] + [2-H] + [2-1]) + [2-C] X 100
SILT [3-C] = 100 - ([3-B] + [3-D])
CLAY [3-D] = ([2-K] - RBLK1) + [2-C] x (1000 + 25) x 100
VC.SAND [3-E] = [2-E] + [2-C] x 100
C.SAND [3-F] = [2-F] + [2-C] x 100
M.SAND [3-G] = [2-G] + [2-C] x 100
F_SAND [3-H] = [2-H] -i- [2-C] X 100
VF.SAND [3-1] = [2-1] -i- [2-C] x 100
C_SILT [3-J] = [3-C] - [3-K]
F.SILT [3-K] = ([2-J] - [2-K]) -t- [2-C] x (1000 + 25) x 100
9.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standard Specification for
Reagent Water, D-1193-77 (reapproved 1983). ASTM, Philadelphia, Pennsylvania.
U.S. Department of Agriculture/Soil Conservation Service. 1984. Soil Survey Laboratory Methods and
Procedures for Collecting Soil Samples. Soil Survey Investigations Report No. 1, U.S.
Government Printing Office, Washington, D.C.
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10.0 pH Determination
10.1 Overview
The pH is defined as the negative logarithm of the activity of hydrogen ions (H+). The H+
activity is a measure of the "effective" concentration of hydrogen ions in solution; it is always equal
to or less than the true concentration of hydrogen ions in solution. Values range from pH 1 to pH
14, with pH 1 most acidic, pH 7 neutral (at 25 *Q, and pH 14 most alkaline. Each pH unit represents
a tenfold change in hT activity (i.e., a pH 4 solution is 10 times more acidic than a pH 5 solution).
When the pH of a sample solution is measured, the hydrogen ions come into equilibrium with
the ion exchange surface (glass) of a calibrated pH electrode, which creates an electrical potential.
This voltage difference is measured by the pH meter in millivolts (mv), which is then converted and
displayed as pH units.
10.1.1 Scope and Application
The following procedure was developed to standardize the measurement of pH in soils. The
method has been written assuming that the Orion Model 611 pH meter and an Orion Ross
combination pH electrode are used (Orion, 1983). The method, however, can be modified for use
with other instrumentation meeting specifications equivalent to those given in Section 10.3.1.
The applicable pH range for soil solutions is 3.0 to 11.0.
10.1.2 Summary of Method
Two suspensions of each soil sample are prepared, one in deionized (DI) water and one in
0.01 M calcium chloride (CaCI2). The pH of each suspension is measured with a pH meter and a
combination electrode. This method is modified from USDA/SCS (1984). The DI water pH is
generally higher than the 0.01 M CaCI2 pH.
10.1.3 Interferences
Factors that normally affect the measurement of pH are (1) electrolyte content of the
extractant; (2) soil-to-solution ratio; (3) temperature and CO2 content of the extractant; (4) errors
that occur with instrument calibration, standard preparation, and liquid junction potential; (5) organic
and inorganic constituents; (6) length of time the soil and solution stand before they are measured;
and (7) technique used in reading the sample suspension.
Soils high in salts, especially sodium, may interfere with the pH reading and the electrode
response time. Clay particles may clog the liquid junction of the pH reference electrode, slowing the
electrode response time; thoroughly rinse the electrode with DI water between sample readings to
avoid this problem. Wiping the electrode dry with cloth, laboratory tissue, or similar materials or
removing the electrode from solution when the meter is not on standby may cause electrode
polarization.
The initial pH of a nonalkaline soil will usually be as much as 0.5 pH unit greater than the pH
taken after the sample has set for 30 minutes or longer. The pH can vary as much as 1.0 pH unit
between the supernatant and soil sediment. Always place the electrode junction at the same
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distance (approximately 3 mm) above the surface of the soil sediment to maintain uniformity in pH
readings.
10.1.4 Safety
Wear protective clothing (laboratory coat and gloves) and safety glasses when preparing
reagents, especially when concentrated acids and bases are used. The use of concentrated acids
should be restricted to a fume hood.
10.2 Sample Collection, Preservation, and Storage
The subsamples for pH measurement are taken from the bulk soil sample after it has been
air dried, homogenized, and tested for moisture content (see sections 4.0 and 8.0). Samples should
be stored at 4 *C until ready for analysis. Preparation of the soil suspensions for pH measurement
is described in Section 10.6.1.
10.3 Equipment and Supplies
10.3.1 Equipment Specifications
1. Digital pH/mV meter, capable of measuring pH to ±0.01 pH unit, potential to ±1 mV, and
temperature to ±0.5 *C. The meter must also have automatic temperature compensation
capability (Orion Model 611 or equivalent).
2. A combination pH electrode, made of high quality, low-sodium glass. At least two
electrodes, one as a backup, should be available. Gel-type reference electrodes must not
be used; an Orion Ross combination pH electrode or equivalent with a retractable sleeve
is recommended.
3. Balance, capable of weighing to ±0.001 g.
4. Balance calibration weights, 3-5 weights covering expected range.
10.3.2 Reagents
1. pH Calibration Buffers (pH 4.0 and 7.0)-Commercially available pH calibration buffers
(National Bureau of Standards [NBS]-traceable) at pH values of 4.0 and 7.0 (two sets
from different sources for calibration and quality control checks).
2. Buffer of pH 4.0 for quality control check standard (QCCS)--The QCCS can be purchased
or it can be prepared from 0.05 M potassium hydrogen phthalate (KHC8H4O4 or KHP). This
buffer must be from a different container or lot than the NBS-traceable standards used
for electrode calibration. Dry KHP for 2 hours at 110 *C, cool to room temperature in a
desiccator. Weigh 10.21 g of KHP, dissolve it in DI water, and dilute the solution to 1.00 L
To preserve the KHP solution, add 1.0 mL of chloroform or one crystal (about 10 mm in
diameter) of thymol per liter of the buffer solution. This solution has the following pH
values at the temperatures given: 3.99 at 15 *C; 4.002 at 20 *C; 4.008 at 25 *C; and 4.015
at 30 *C.
3. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
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4. Calcium hydroxide [Ca(OH)2]--Dissolve 0.185 g Ca(OH)2 in DI water and dilute to 1 L
5. Hydrochloric acid (HCI)-Dilute 1 ml concentrated HCI to 1 L with DI water.
6. Stock calcium chloride solution (CaCI2), 1.0 M--Dissolve 55.49 g of anhydrous CaCI2 or
73.51 g of CaCI2«2H2O in DI water and dilute to 500 mL.
7. Calcium chloride, 0.01 M CaCI2-Dilute 20 ml of stock 1.0 M CaCI2 to 2.0 L with DI water.
If the pH of this solution is not between 5 and 6.5, adjust the pH by addition of dilute
Ca(OH)2 or HCI, as needed.
8. Potassium chloride (3 M)--Dissolve 224 g KCI in DI water and dilute to 1 L
9. Potassium chloride (0.1 M).
10. Sodium hydroxide (NaOH) pellets.
10.3.3 Consumable Materials
1. Beakers, plastic, or paper containers, 50-mL
2. Glass stirring rods or disposable stirrers, one per sample.
3. Weighing pans, disposable.
4. Forms-Form 4 pH in water, Form 5 pH in 0.01 M calcium chloride, Form QC-4, and Form
QC-5 (Appendix B, figures B-15 through B-18, respectively).
10.4 Calibration and Standardization
NOTE: For storage and readings, the electrode need only be immersed to cover the liquid
junction of the reference electrode (typically about 3 mm). Rinse the electrode with DI
water between each sample and each buffer to prevent solution carryover. Do not rub
or blot electrode dry because this may produce a static electric charge and thereby
polarize the electrode.
10.4.1 Instrument Preparation
1. Plug in the instrument and verify that the control knob is on "STD BY." Allow at least 30
minutes for instrument warm-up prior to use.
NOTE: If instrument is used frequently, leave on and in "STD BY" mode between uses.
2. Connect the combination electrode to the meter. Consult the pH electrode manual for the
proper procedure.
3. Verify that the level of reference filling solution (3 M KCI) in the electrode is just below the
fill hole and that the fill hole is uncovered during measurement (slide the plastic sleeve
down).
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4. Calibrate the meter for temperature weekly using a two-point standardization (one point at
approximately 5 °C to 10 °C and the other point at room temperature).
a. Room temperature-Place the electrode and an NBS-traceable thermometer into DI water
which is at room temperature. Swirl the electrode for 5 to 10 seconds.
b. Turn the knob on the meter to "TEMP." Using a small screwdriver, turn the "TEMP ADJ"
screw on back of the pH meter to adjust the display to the temperature reading of the
thermometer.
c. Cold temperature-Place the probe and the NBS-traceable thermometer into a 250-mL
beaker containing cold DI water (5 to 10 °C). Repeat Step b by adjusting the display
with the "TEMP Slope" screw on the back of the meter.
d. Continue steps a through c until no further adjustments are necessary and record all
values in the logbook.
10.4.2 Calibration with Buffers
1. Check the meter temperature calibration daily with a beaker of room temperature DI water
and an NBS-traceable thermometer. If the display differs from the NBS-traceable
thermometer by more than 1.0 °C, complete adjustments as described in Section 10.4.1,
above.
2. Pour fresh pH 7.00 and pH 4.00 buffer solutions into labeled 50-mL beakers (one "RINSE",
one "CALIBRATION", and one "CHECK" beaker for each buffer). Rinse all beakers three
times with buffer solutions and fill with the appropriate buffer solutions.
3. Rinse the electrode with DI water. Place the electrode into the pH 7.00 "RINSE" beaker and
swirl for 40 seconds. Place the electrode into the "CALIBRATION" beaker, turn the knob to
"pH", swirl for 30 to 60 seconds (or until the pH reading is stable), and read the value on the
display. Consult the pH-temperature chart, Table 10-1. Use the "CALIBRATE" knob to adjust
the pH reading on the meter to the theoretical pH of the buffer solution at the appropriate
temperature.
4. Repeat Step 3 for pH 4.00 buffer using the "% SLOPE" knob to adjust the pH reading.
5. Repeat steps 3 and 4 until both the pH 7.00 and the pH 4.00 buffers agree with the
theoretical pH of the buffer solution at the appropriate temperature.
6. Check the standardization using the buffer solutions in the "CHECK1 beakers. If the values
differ by more than ±0.03 units from the theoretical value, repeat the standardization
process. When the meter standardization is acceptable, record the pH and temperature
readings for each buffer solution in the pH logbook.
10.4.3 Maintenance
1. Weekly, drain the 3 M KCI filling solution from the electrode using a disposable pipet with
Teflon tubing attached.
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2. Refill the electrode chamber with the 3 M KCI filling solution and rinse by inverting the
electrode. Drain the solution as in Step 1.
Table 10-1. pH Value* of Buffere at Varloue Temperature*
Temperature
25 °C
1.68
3.78
4.01
6.86
7.00
7.41
9.18
10.01
0°C
1.67
3.86
4.00
6.98
7.11
7.53
9.46
10.32
5°C
1.67
3.84
4.00
6.95
7.08
7.50
9.40
10.25
10 °C
1.67
3.82
4.00
6.92
7.06
7.47
9.33
10.18
20 °C
1.67
3.79
4.00
6.87
7.01
7.43
9.23
10.06
30 °C
1.68
3.77
4.02
6.85
6.98
7.40
9.14
9.97
40 °C
1.69
3.75
4.03
6.84
6.97
7.38
9.07
9.89
3. Refill the electrode with the filling solution to just below the fill hole.
4. Gently spin the electrode overhead for approximately 1 minute by the leader to remove any air bubbles. Be
careful to stand clear of any obstacles when swinging the electrode.
10.4.4 pH Meter Electronic Checkout
NOTE: This procedure should be performed whenever a new pH meter is set up or when
calibration problems occur.
1. Connect the shorting strap as outlined in the Orion pH meter manual.
2. Turn the "TEMP ADJ" and "TEMP SLOPE1 screws fully counterclockwise and record the
display pH value (turn knob to "pH" position).
3. Turn the "TEMP SLOPP' screw 7.5 turns clockwise and record the display pH value. The
difference between the "TEMP SLOPE" value in Step 2 and Step 3 should be between 7.0 and
15.0.
4. Turn the "TEMP ADJ" screw until a value between 50.0 ± 0.1 appears on display.
5. Press the test button. A value of 42.2 ± 2.0 should appear on the display when the knob
is in the "TEMP" position. If this value is not displayed, keep depressing the test button and
use the "TEMP SLOPE" screw to adjust the reading to 4.0 ± 1.0. Release the test button and
use the "TEMP ADJ" screw to obtain a reading of 50.0 ±0.1. Press the test button again.
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The reading should be 42.2 ± 2.0. Repeat this procedure several times if the value is not
in range.
10.4.5 Electrode Etching Procedure
The electrode etching procedure is described in Section 6.4.5.
10.5 Quality Control
Log all quality control (QC) data on forms QC-4 and QC-5 (Appendix B, figures B-17 and B-18);
refer to Section 3 for additional information concerning these internal quality control checks.
Reagent Blanks-Analyze one blank of each suspension solution. The blank used for each pH
method is the reagent used: 01 water or 0.01 M CaCI2. The measured pH of each blank should fall
between 4.5 and 7.5 pH units.
ffep//c3tes--Or\e sample from each batch should be analyzed in triplicate for pH in each of the
DI water and 0.01 M CaCI2 solutions. The standard deviation for each set of three replicates should
be 0.10 pH units or less.
Quality Control Check Sample (QCCS)~k pH 4.00 standard from a different preparation source
or lot number than that used for the calibration is used as the QCCS. Analyze a QCCS before
beginning analysis of routine samples, at specified intervals thereafter, e.g., after every ten samples
and after completion of routine sample analysis for the day. Measured values of each QCCS should
be 4.00 ± 0.05. If the QCCS does not meet this criterion, recalibrate the electrode and repeat the
QCCS measurement using a fresh QCCS. If acceptable results still cannot be obtained: check
electrode for clean reference junction, check wiring straps into meter, check for static electricity, and
check to see if enough filling solution is contained within the electrode. If a problem still persists,
replace electrode or meter, or both.
QC Audit Sample (QCASJ-The QCAS should fall within the accuracy window provided by the
quality assurance (QA) manager.
10.6 Procedure
NOTE: The figures in the square brackets, [ ], represent the column of the appropriate form
where the data are recorded.
10.6.1 Preparing Soil Suspensions
1. Weigh 20.0 g of air-dry mineral soil into a beaker and add 20.0 mL of DI water; for
organic soils, use 5.0 g of soil and 25.0 mL of DI water. Log exact sample weight [4-B]
and volume [4-C].
2. Allow soil to absorb the liquid without stirring.
3. Stir the mixture for 10 seconds and allow mixture to sit for 15 minutes.
4. Repeat Step 3 three times.
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5. Repeat steps 1 through 4, replacing the DI water with 0.01 M CaCI2. Log sample weight
[5-B] and volume of 0.01 M CaCI2 [5-C].
10.6.2 pH Measurements
1. After the final stirring, allow the suspension to settle for at least 1 minute. Place the pH
electrode in the supernatant of the soil suspension.
For mineral soils, the reference junction should be below the solution surface and above
the soil-solution interface.
Some organic soils swell upon wetting, so there is no free water available. As long as
the reference junction is below the surface of the organic material, an acceptable,
repeatable reading generally is attained. When the reading is stable, record pH to the
nearest 0.01 pH unit.
2. Report the pH of the soil:DI water suspension, [4-D] and the soil:0.01 M CaCI2 suspension
[5-D], for each sample.
3. After measurements are completed, store the electrode in 0.1 M KCI storage solution. Do
not let the sensing element and reference junction dry out. The level of the storage
solution should be one inch below the filling solution level to prevent influx of the storage
solution. Check periodically that the electrode reservoir is full of filling solution.
10.7 Calculations
No calculations are required to Obtain pH values. Replicate measurements of the same
sample or of duplicate samples should not be averaged.
10.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards Vol. 11.01,
Standard Specification for Reagent Water, D-1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
Orion Research Incorporated. 1983. Institutional Manual - Model 611 pH/millivolt meter. Orion,
Cambridge, Massachusetts.
U.S. Department of Agriculture/Soil Conservation Service. 1984. Soil Survey Laboratory Methods and
Procedures for Collecting Soil Samples. Soil Survey Investigations Report No. 1, U.S.
Department of Agriculture, U.S. Government Printing Office, Washington, D.C.
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//. Cation Exchange Capacity
11.1 Overview
Cation exchange capacity (CEC), usually expressed in milliequivalents (meq) per 100 g of soil,
is a measure of the quantity of readily exchangeable cations neutralizing negative charge in the soil
(Rhoades, 1982). Negative charge in the soil can be derived from several sources which fall into two
categories: permanent and pH dependant (or variable) charge. Permanent charge sites are the
result of isomorphic substitution within the crystal structure of the layer silicate minerals which are
commonly thought of as clay minerals. Permant charge CEC is independent of pH, electrolyte
concentrations, ion valences and the dielectric constant of the medium which influence the
contribution of the overall CEC from the pH dependant charges. The pH dependant CEC is derived
from broken bonds at mineral edges, dissociation of acidic functional groups in organic matter and
sesquioxides present in the soil, and preferential adsorption of certain ions on the charged particle
surfaces. In general, as the pH electrolyte concentration, dielectric constant of the medium, and the
ion valences increase, the net contribution of pH dependant charge to the overall CEC increases.
A close approximation of the CEC can be made by the summation of the exchangeable base
cations of Caz+, Mg2+, Na+, and K+ and the exchangeable acidity as determined by BaCI2-TEA
extraction or the addition of exchangeable Al extracted by KCI (USDA/SCS, 1972).
//. /. / Scope and Application
Two saturating solutions are used for CEC determination. Ammonium acetate (1.0 N NH4OAc)
buffered at pH 7.0 yields a CEC which is close to the total cation exchange capacity for a specific
soil. This saturating solution is commonly used for soil comparisons. In acid soils, this estimate
results in a high CEC value because of adsorption of NH4 ions to the pH-dependent exchange sites
that exist above the soil's natural pH level. The overestimation will not occur when an unbuffered
saturating solution of ammonium chloride (1.0 N NH4CI) is used. The NH4CI CEC has been termed
"effective" CEC (i.e., that which occurs at field pH and is of greater importance because it is a more
realistic estimate of CEC than the total CEC by NH4OAc). The two saturating solutions are retained
for the exchangeable cation determinations (sections 12.0 and 13.0). This method has been written
assuming use of a mechanical extractor.
11.1.2 Summary of Method
The soil sample is saturated with NH4 from a solution of NH4OAc or NH4CI. Excess NH4 is
removed by ethanol rinses. The NH4 is displaced by Na+ and is analyzed by one of three methods:
automated distillation-titration, manual distillation-automated titration, or ammonium displacement-
flow injection analysis. The entire procedure is repeated with a fresh aliquot of sample and a
solution of NH4CI as the NH4 source. These methods are based on Doxsee (1985), Rhoades (1982),
and USDA/SCS (1984).
11.1.3 Interferences
Inconsistency in the NH4 saturating and rinsing steps is the greatest source of error. Soils
containing an abundance of minerals, such as biotite and muscovite which may contain inter-lattice
NH4, may produce artificially high results. The use of a mechanical extractor minimizes
inconsistency.
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11.1.4 Safety
Wear protective clothing (laboratory coat and gloves) and safety glasses when preparing
reagents, especially when concentrated acids and bases are used. The use of concentrated acids
and hydroxide solutions should be restricted to a fume hood.
11.2 Sample Collection, Preservation, and Storage
The subsamples for CEC determination are taken from the bulk soil sample after it has been
air dried, homogenized, and tested for moisture content (see sections 4.0 and 8.0). Samples should
be stored at 4 "C until ready for analysis. Preparation of the saturating solutions is described in
Section 11.3.3.
11.3 Equipment and Supplies
11.3.1 Apparatus for Saturation Procedure
1. Mechanical extractor, 24-place (see Figure 11-1).
2. Reciprocating shaker.
3. Balance, capable of weighing to 0.01 g.
4. Balance calibration weights, 3-5 weights covering expected range.
5. Wash bottle.
11.3.2 Apparatus for Analysis
The apparatus and equipment needed are specific to the selected analytical method. It is not
necessary to have equipment for all three analytical methods.
11.3.2.1 Ammonium Displacement-Flow Injection-
1. Flow injection analyzer (FIA), Lachat or equivalent, modified for ammonium chemistry with
630-nm interference filter and consisting of:
a. Sampler.
b. Analytical manifold with 200-//L sample loop.
c. In-line heater.
d. Colorimeter equipped with a 10-mm flow cell.
e. Printer.
2. Balance, capable of weighing to 0.001 g.
3. Balance calibration weights, 3-5 weights covering expected range.
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11.3.2.2 Automated Distillation-Titration-
1. Steam distillation-titration apparatus, Kjeltec Auto 1030 Analyzer, or equivalent.
2. Printer, Alphacom 40, or equivalent.
3. Digestion tubes, 250-mL, straight neck.
4. Balance, capable of weighing to 0.1 g.
5. Balance calibration weights, 3-5 weights covering expected range.
6. Policeman, rubber.
11.3.2.3 Manual Distillation/Automated Titration-
1. Automatic titrator with autosampler, Metrohm or equivalent.
2. Kjeldahl flasks, 800-mL
3. Balance, capable of weighing to 0.1 g.
4. Balance calibration weights, 3-5 weights covering expected range.
5. Policeman, rubber.
11.3.3 Reagents and Consumable Materials for Saturation Procedure
1. Washed analytical filter pulp, Schleicher and Schuell, No. 289 (see Section 11.6.1 for
washing procedure).
2. Glacial acetic acid (HC2H3O2).
3. Ammonium hydroxide (NH4OH), concentrated.
4. Ammonium acetate (NH4OAc), reagent grade, 1 N, pH 7.0--To 15 L deionized water (DI) in
a 20-L bottle, add 1,388 g crystalline ammonium acetate and dissolve by stirring; allow
to come to ambient temperature, then dilute to 18 L with DI water; adjust to pH 7.0 with
acetic acid or ammonium hydroxide.
5. Ammonium chloride (NH4CI), reagent grade, 1 N-Dissolve 535 g in DI water and dilute to
10 L
6. Ethanol (C2H5OH), 95 percent, U.S.P.
7. Nessler's reagent-
a. Add 4.56 g potassium iodide (KI) to 30-mL DI water in a beaker. Add 5.68 g mercuric
iodide (HgI2). Stir until dissolved.
b. Dissolve 10 g NaOH in 200-mL DI water.
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c. Transfer NaOH solution to 250-mL volumetric flask. Add Hg solution slowly. Dilute
to volume and mix thoroughly. Solution should not contain a precipitate. It can be
used immediately.
8. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
9. Syringes, disposable, 60-mL polypropylene (use one sample tube, one reservoir tube, and
one tared extraction syringe for each sample).
10. Rubber tubing, 1/8 x 1/4 inch (for connecting syringe barrels).
11. Bottles, linear polyethylene (LPE), 25-mL.
12. Tubes, glass, centrifuge or culture, with caps, 25-mL.
13. Weighing pans, disposable.
11.3.4 Reagents and Consumable Materials for Analysis
The reagents and consumable materials needed are specific to the selected analytical
procedure. It is not necessary to have the reagents and materials for all three analytical
procedures.
11.3.4.1 Ammonium Displacement-Flow Injection Analysis--
The reagents and consumable materials used depend on recommendations of the
manufacturer of the FIA and may vary by make and model.
1. Hydrochloric acid, 0.1 N--Purchased or prepared by the following procedure: Add 150 mL
concentrated HCI to approximately 15 L DI water, dilute to 18 L Standardize 0.1 N HCI
by titration against dried primary standard grade sodium carbonate to the methyl orange
end-point.
2. Nitroferricyanide reagent-Dissolve 40 g potassium sodium tartrate (KNaC4H4O6) and 30
g sodium citrate (Na3C6H5O7«2H2O) in 500 ml DI water. Add 10 g sodium hydroxide
pellets (NaOH). Add 1.5 g sodium nitroferricyanide (Na2Fe(CN)5NO2H2O), dilute to 1.00
L, and mix well. Store in a dark bottle. Prepare fresh solution monthly.
3. Sodium hypochlorite reagent-Dissolve 20 g sodium hydroxide and 20 g boric acid in 150
mL of DI water. Add 800 mL 5 percent solution NaOCI. Dilute to 1.00 L with DI water.
Store in a dark bottle. Prepare fresh solution monthly.
4. Sodium phenate reagent-Dissolve 95 mL of 88 percent liquified phenol in 600 mL DI
water. While stirring, slowly add 120 g NaOH. Cool. Add 100 mL ethanol and dilute to
1.00 L. Store in a dark bottle.
5. Nitrogen standard solution, 1,000 mg NH4-N/L-Dissolve 3.819 g ammonium chloride
(NH4CI), dried at 105 *C, in DI water and dilute to 1.00 L
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6. Working standards-Pipet 15.0, 10.0, 6.0, and 2.0 ml_ of the nitrogen standard solution,
above, into 100-mL volumetric flasks. Bring to volume with 0.1 N HCI. This will yield 150,
100, 60, and 20 mg NH4-N/L working standards. Pipet 5 mL of the 100 mg NH4-N/L
working standard into a 100-mL volumetric flask and dilute to volume with 0.1 N HCI. This
provides a 5 mg NH4-N/L working standard. Prepare fresh working standards weekly.
7. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
8. Weighing pans, disposable.
9. Forms-Form 6A, cation exchange capacity-ammonium acetate (flow injection analysis),
Form 7 A, cation exchange capacity-ammonium chloride (flow injection analysis), Form QC-
6A, and Form QC-7A (Appendix B, figures B-19, B-21, B-23, and B-25, respectively).
11.3.4.2 Automated Distillation-Titration-
1. Sodium chloride (NaCI).
2. Antifoam, silicone spray bottle.
3. Hydrochloric acid (HCI), 0.10 N, standardized-see Section 11.3.4.1, Step 1.
4. Boric acid (H3BO.j), 4 percent (w/v) aqueous solution-Add 720 g boric acid to about 4 L
DI water in a large stainless steel beaker. Heat to near boiling and stir until crystals
dissolve. Add to a 5-gallon Pyrex bottle about 12 L DI water. Transfer hot solution
through a large polyethylene funnel into the bottle. Dilute to 18 L with DI water and mix
well.
5. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
6. Compressed air.
7. Weighing pans, disposable.
8. Forms-Form 6B, cation exchange capacity-ammonium acetate (titration method), Form
7B, cation exchange capacity-ammonium chloride (titration method), Form QC-6B, and
Form QC-7B (Appendix B, figures B-20, B-22, B-24, and B-26, respectively).
11.3.4.3 Manual Distillation-Automatic Titration-
1. Sodium chloride (NaCI).
2. Antifoam mixture-Mix equal parts of mineral oil and octanol.
3. Boric acid (HgBOJ, 4 percent-see Section 11.3.4.2, Step 4.
4. Hydrochloric acid (HCI), 0.1 N-see Section 11.3.4.1, Step 1.
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5. Sodium hydroxide (NaOH), 1 N--Add 500 ml 50 percent NaOH solution to 8 L of DI water
in a 9.5-L Pyrex solution bottle. Dilute to 9 L with DI water and mix well.
6. Zinc, granular.
7. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
8. Compressed air.
9. Beakers, plastic disposable, 250-mL
10. Weighing pans, disposable.
11. Forms-Form 6B, cation exchange capacity-ammonium acetate (titration method), Form
7B, cation exchange capacity-ammonium chloride (titration method), Form QC-6B, and
Form QC-7B (Appendix B, figures B-20, B-22, B-24, and B-26, respectively).
11.4 Calibration and Standardization
11.4.1 Flow Injection Analysis Calibration
For the FIA, use standards containing 0, 5, 20, 60, 100, and 150 mg NH4-N/L to develop a
calibration curve. A regression of the standard curve should have an intercept close to zero. Air
bubbles can produce sharp sudden peaks which destroy the calibration curve. In the event of air
bubbles, the calibration curve and all samples analyzed since the last quality control check sample
(QCCS) must be reanalyzed. Standard values should not vary by more than 5 percent relative
standard deviation (%RSD). Standardization is accomplished through use of the mechanical
extractor, volumetric glassware, and repipets (automatic pipettors). Operation of repipets and
calibration of balances are described in Appendix A, General Laboratory Procedures.
11.4.2 Titration Calibration
Titrants used in the automated titrations are calibrated prior to analysis to establish the
normality. The normality is checked weekly. Should the check value differ from the normality by
more than 5 percent, two additional checks are run and the mean of the three check values is used
as the normality. The same standard titrant should be used for all samples within a batch.
11.5 Quality Control
Log all QC data on forms QC-6A, QC-6B, QC-7A, or QC-7B (Appendix B, figures B-23 through
B-26, respectively); refer to Section 3.0 for additional information concerning these internal quality
control checks.
Calibration B/anks-Calibration blanks should be analyzed before the initial sample analysis,
at specified intervals thereafter (e.g., after every ten samples) and after the last sample of each
batch. If any blank is higher than the contract required detection limit (CRDL) listed in Table 3-2,
check the system and reanalyze all samples since the last acceptable calibration blank.
Reagent B/anks-Three reagent blanks, carried through the extraction procedure, are analyzed
with each batch of samples for both the NH4OAc and NH4CI exchange. The calculated concentration
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of each blank should be less than or equal to 1.05 mg N/L for FIA (0.15 meq/L) or 0.0075 meq for
titrations (0.15 meq/L).
ffep/icates-One sample from each batch should be extracted and analyzed in duplicate. The
%RSD should meet the limits in Table 3-3.
Quality Control (QC) Standards-One detection limit quality control check standard (DL-QCCS)
should be analyzed for each exchange during each batch of samples. This standard should be 5.0
mg NH4-N/L for FIA or 0.03 meq for titrations. Measured values should be within 20 percent of the
known value. While permitting monitoring of instrumental detection limits, it does not replace the
need to formally determine detection limits on a periodic basis (see Section 3.2.1).
QCCSs of concentrations at about mid-calibration range of the samples being analyzed should
be measured before the first sample, at specified intervals thereafter (e.g., every tenth sample) and
after the last sample of each batch of samples for both exchanges. Measured values for each
QCCS should be within 10 percent of the known value.
Matrix Spikes-Use a solution of NH4CI or (NHJ2SO4 as the spiking solution. For FIA, the final
solution may be split and the matrix spike added to one of the splits. For distillation-titration, a
second sample must be processed and the matrix spike must be added to the sample just prior to
distillation. Recovery should be 90 to 110 percent of the spike concentration.
QC Audit Sample (QCAS)-Tbe QCAS should fall within the accuracy windows provided by the
quality assurance (QA) manager.
11.6 Procedure
Before starting the analytical procedures, valid instrumental detection limits (IDLs) are to be
established, the required labware should meet the cleaning criteria described in Appendix A, General
Laboratory Procedures, and the samples must have been properly prepared (see Section 4.0).
Analyses should be performed as described below for NH4OAc, then repeated for NH4CI. All data
should be logged following the procedures given in Section 3.0.
11.6.1 Pulp Washing
NOTE: Commercial filter pulps often are contaminated and will have to be washed.
1. Prepare sample tubes by tightly compressing a 0.5-g ball of filter pulp into bottom of
syringe barrel with a modified plunger. Modify the plunger by removing the rubber portion
of the plunger, and cut off the plastic protrusion.
2. Add 50 mL 0.1 N HCI to the syringe containing the pulp and extract rapidly.
3. Add 50 mL DI water to the syringe containing the pulp and extract rapidly.
4. Repeat Step 3 again.
5. Remove any excess solution from the washed pulp by applying gentle suction to the
syringe tip. Proceed immediately with an extraction.
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11.6.2 Extraction
NOTE: Figures within the square brackets, [ ], represent the form number and column in which the
data are entered.
1. For mineral soils, weigh 5.00 g air-dry soil, place in sample tube, and record exact weight
[6A-B] or [6B-B] for NH4OAc, [7A-B] or [7B-B] for NH4CI. Place sample tube in upper disc
of extractor and connect to inverted, tared extraction syringe, the plunger of which is
inserted in the slot of the stationary disc of the extractor. Fill the syringe to the 25-ml
mark with NH4OAc. Stir sample and NH4OAc with glass stirring rod for 15 seconds, rinse
rod with NH4OAc, and fill syringe to the 30-mL mark. Let stand for 20 minutes.
For organic soils, weigh 1.25 g of air-dried soil into a small glass tube [6A-B] or [6B-B]
for NH4OAc, [7A-B] or [7B-B] for NH4CI. Add 2 mL ethanol as a wetting agent. (If the
organic soil wets easily, it is not necessary to add the ethanol.) When the soil is
moistened, add 15 mL NH4OAc, cap, and shake for one hour on a reciprocating shaker.
Place sample tube in upper disc of extractor and connect to inverted, tared extraction
syringe, the plunger of which is inserted in the slot of the stationary disc of the extractor.
Then quantitatively transfer the sample and NH4OAc to the sample tube and fill to the 25-
mL mark with NH4OAc. Let stand for 20 minutes.
NOTE: Up to 35-mL may be used for transfer; see Step 2.
The exact sample weights are also recorded in column B, forms 8 through 11 for the
ammonium acetate exchanges (in Section 12.0) and in column B, forms 12 through 17 for
the ammonium chloride exchanges (in Section 13.0).
2. Put reservoir tube on top of sample tube; extract rapidly until NH4OAc is at a depth of 0.5
to 1.0 cm above sample. Turn off extractor. Add about 45 mL NH4OAc to reservoir tube,
turn on extractor, and extract overnight or for approximately 16 hours. Do not allow the
soil to dry between the time the extractor is turned off and back on.
NOTE: If 35 mL are used in Step 1, reduce 45 mL to 35 mL. Total NH4OAc or NH4CI used
during extraction should be approximately 70 mL.
3. The next morning, switch off extractor and pull plungers down as far as extractor will
allow. Disconnect syringes from sample tubes, leaving rubber connectors on sample
tubes. Weigh each syringe containing the NH4OAc extract to the nearest 0.01 g. The final
weight and tare weight are used to calculate the volume of ammonium acetate extract
(Section 12.0), according to the formula in Section 12.7. Final volumes are recorded in
column C on forms 8 through 11 for NH4OAc and on forms 12 through 16 for NH4CI.
4. Mix the extract in each syringe by shaking manually. Rinse the appropriately labeled
polyethylene bottle twice with small volumes of the extract solution, then fill the bottle
with extract solution and discard the excess. This solution is reserved for analysis of
exchangeable cations as described in Section 12.0.
5. Return upper 2-disc unit to starting position. Attach the syringes to the sample tubes,
and rinse the sides of sample tubes with ethanol from a wash bottle. Fill sample tubes
to the 20-mL mark, stir, and let stand for 15 to 20 minutes. Place reservoir tube in sample
tube. Extract rapidly until the level of ethanol is 0.5 to 1.0 cm above sample. Turn off
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extractor and add enough ethanol to the reservoir to ensure an excess over the capacity
of the syringe. Extract for 45 minutes.
6. After the extractor has stopped, turn off the switch, pull the plungers down, remove
syringes, and discard the ethanol wash. Return the upper unit of the extractor to starting
position, reattach syringes to the sample tube, fill reservoir tubes with about 45 ml_
ethanol, and extract a second time for approximately 45 minutes. When extractor has
stopped, remove syringes and discard ethanol. After the second ethanol extraction,
collect a few drops of ethanol extract on a spot plate. Test for residual NH« in each
sample by adding four drops of Nessler's reagent to one drop of solution. If the test is
positive (i.e., orange endpoint) repeat another ethanol extraction of the affected samples
and test by using Nessler's reagent until a negative test is obtained. Proceed to Section
11.6.3 if using FIA, to Section 11.6.4 if using automated distillation, or to Section 11.6.5 if
using manual distillation.
7. Repeat steps 1 through 6 using ammonium chloride as the exchange solution.
11.6.3 Analytical Procedure Using FIA
1. Add 50 ml of 0.1 N HCI and extract at setting of 10 (approximately one hour) and record
volume [6A-C] or [7A-C].
2. Disconnect syringes and save the HCI extract for FIA analysis.
3. Operate the FIA according to manufacturer's instructions.
4. Read mg NH4-N/L; if concentrations exceed calibration standards, dilute in the instrument
calibration range and reanalyze.
5. Record data as follows:
Actual Exchange Aliquot Volume Diluted Volume Instrument Reading
CECOAC [6A-D] [6A-E] [6A-F]
CEC.CL [7A-D] [7A-E] [7A-F]
11.6.4 Analytical Procedure using Automated Distil/ation-Titration
1. Remove sample tubes and quantitatively transfer each sample to a 250-mL digestion tube.
To remove the sample, blow the filter pulp and soil out of the syringe by using a gentle
flow of compressed air. Wash with a minimum of DI water. Use a rubber policeman to
complete the transfer.
2. Add 6 to 7 g sodium chloride to the digestion tube, spray silicone antifoam solution into
the digestion tube and connect it to the Kjeltec Auto 1030 Analyzer.
3. Follow instruction manual regarding safety and operation of the analyzer and titrate to
a pH 4.60 endpoint.
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4. Read mL titration and record with the normality of titrant:
NH4OAc, [6B-C], [6B-D]; NH4CI [7B-C], [7B-D].
11.6.5 Analytical Procedure using Manual Distillation-Automated Titration
1. Transfer sample to an 800-mL Kjeldahl flask using the procedure described in Section
11.6.4, Step 1.
2. Add 400 ml DI water, 10 g NaCI, 5 drops antifoam mixture, 1 to 2 g granular zinc, and 40
mL 1.0 N NaOH.
3. Set up Kjeldahl distillation apparatus and distill until 175-180 mL of distillate is collected
in a 250-mL plastic beaker containing 50 mL of 4 percent boric acid solution.
4. Transfer plastic beaker to distillation apparatus and operate according to manufacturer's
instructions.
5. Read mL titration and record with the normality of titrant as described in Section 11.6.4,
NH4OAc: [6B-C], [6B-D]; NH4CI: [7B-C], [7B-D].
11.7 Calculations
NOTE: Designations within the square brackets, [ ], represent the Form number and column in
which the data are entered on forms 6A, 7A, 6B, and 7B (Appendix B, figures B-19, B-21. B-
20, and B-22).
//. 7.1 Flow Injection Analysis
CEC (meq/100 g) = {([Final Sol. Vol.] x [Inst. Reading]) x ([Total Diluted Vol.] +
[Aliquot Vol.]) x 1 L} + {[1,000 mL x 1 meq + 14 mg x 1] +
(sample wt. x (1-[MOIST]) + (100 + [MOIST])}
CEC OAC [6A-G] = {([6A-C] x [6A-F]) x ([6A-E] + [6A-D]) x 1} + {[6A-B] x (1 - [1-D])
+ (100 + [1-D])}
CEC CL [7A-G] = {([7A-C] X [7A-F]) x ([7A-E] + [7A-D]) X 1} + {[7A-B] x (1 - [1-D])
+ (100 + [1-D])}
11.7.2 Titration
[CEC (meq/100 g)] = {[Titrant Volume] x [Normality] x 1} + {[sample wt.] x (1 -
[MOIST]) + (100 + [MOIST]) x 100}
CEC OAC [6B-E] = {[6B-C] x [6B-D] x 1} + {[6B-B] x (1 - [1-D]) + (100 + [1-D]) x
100}
CEC CL [7B-E] = {[7B-C] x [7B-D] x 1} + {[7B-B] x (1 - [1-D]) + (100 + [1-D]) x
100}
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11.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specification for Reagent Water, D-1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
Doxsee, K. 1985. Cation Exchange Capacity in Nursery Soils Using FIA (Flow Injection Analysis).
Am. No. 1503-15. Weyerhaeuser Technology Center, Research Division, Tacoma, Washington.
Rhoades, J. D. 1982. Cation Exchange Capacity, pp. 149-158. In: Methods of Soil Analysis: Part
2-Chemical and Microbiological Properties, Second Edition, A. L Page, R. H. Miller, and D. R.
Keeney (eds.). American Society of Agronomy, Inc./Soil Science Society of America, Inc.,
Madison, Wisconsin.
U.S. Department of Agriculture/Soil Conservation Service. 1972. Procedures for Collecting Soil
Samples and Methods of Analysis for Soil Surveys. Soil Survey Investigations Report No. 1,
U.S. Department of Agriculture. U.S. Government Printing Office, Washington, D.C.
U.S. Department of Agriculture/Soil Conservation Service. 1984. Soil Survey Laboratory Methods and
Procedures for Collecting Soil Samples. Soil Survey Investigations Report No. 1, U.S.
Department of Agriculture. U.S. Government Printing Office, Washington, D.C.
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12.0 Exchangeable Cations in Ammonium Acetate
12.1 Overview
The exchangeable cations (Ca2+, Mg2+, K+, and Na+) in the soil can be used to estimate the
ability of a soil to buffer acidic deposition. Ammonium chloride and buffered ammonium acetate are
used to extract exchangeable base cations at pH values near the soil pH and at the buffered pH of
7.0, respectively.
Base saturation is defined as the sum of exchangeable base cations divided by the cation
exchange capacity (CEC) and is expressed as a percentage. Cation exchange sites not occupied
by base cations are assumed to be occupied by acidic cations such as hydrogen and aluminum.
CEC is a measure of the buffering capacity of the soil. Base saturation relates to how much
buffering capacity remains in the soil. Exchangeable acidity is a measure of the amount of
exchangeable acidic cations on the soil cation exchange complex
12.1.1 Summary of Method
Previously prepared extracts from the CEC procedure (Section 11.0) are analyzed for calcium,
magnesium, potassium, and sodium. Once the concentration of each cation in the soil extract is
determined, the cation concentrations in the original soil sample may be calculated.
Atomic absorption spectroscopy (AA) can be used to measure calcium, magnesium,
potassium, and sodium. A light beam from a hollow cathode lamp, whose cathode is made of the
element to be determined, is directed through the flame into a monochromator and onto a detector
that measures the amount of light passing through the flame. Absorption depends upon the
presence of free, unexcited, ground state atoms in the flame. Since the wavelength of the light
beam is characteristic only of the cation being determined, the light energy absorbed by the flame
is a measure of the concentration of that cation in the extract. A complete discussion of AA
methods is provided in Appendix C.
Inductively coupled plasma spectroscopy (ICP) can be used to measure calcium, magnesium,
and sodium. Samples are nebulized to produce an aerosol. The aerosol is transported by an argon
carrier stream to an inductively coupled argon plasma, which is produced by a radio frequency
generator. In the plasma (which is at a temperature of 6,000 to 10,000 *K) the analytes in the
aerosol are atomized, ionized, and ionic emission spectra is produced. The spectra from all analytes
are dispersed by a grating spectrometer and the intensities of the lines are monitored by photo-
multiplier tubes. The photocurrents from the photomultiplier tubes are processed by a computer
system. The signal is proportional to the analyte concentration and is calibrated by analyzing a
series of standards (U.S. Environmental Protection Agency [USEPA], 1983; Fassel, 1982). A thorough
discussion of ICP methods is provided in Appendix D.
Emission spectroscopy (ES) can be used to measure potassium and sodium. The sample is
aspirated into a gas flame and excitation is carried out under carefully controlled and reproducible
conditions. The desired spectral line is isolated by the use of interference filters or by a suitable
slit arrangement in light-dispersing devices such as prisms or gratings. The intensity of light is
measured by a phototube potentiometer or other appropriate circuit. The intensity of light at the
appropriate wavelength (e.g., 589 nm for Na4) is approximately proportional to the concentration of
the element. A discussion of ES methods is provided in Appendix E.
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12.1.2 Interferences
Three types of interferences, spectral, chemical, and physical, can be identified for the
analytical portion of the method. These vary in importance depending on the particular analytical
procedure chosen. Additional details of these interferences and means for their obviation,
elimination, or compensation are provided in appendices C, D, and E.
Spectral interferences are generally caused by spectral overlap from another element or
background contributions. These interferences can usually be corrected by monitoring and
compensating for the effect of interfering elements, selecting another wavelength, correcting
background effects, or using a narrower slit width.
Chemical interferences are often caused by the cations forming molecular compounds instead
of dissociated ions. This interference, most pronounced with the multivalent ions (such as Ca2+ and
Mg2+), is negligible with the ICP technique. This interference is often corrected by the addition of
lanthanum or lithium or by the avoidance of anions such as sulfate and phosphate.
The most common physical interference in the analysis of soils exchange solutions is salt
build-up clogging the burner or nebulizer. Although dilution will reduce this problem, it will also
change the matrix and any effect it may have on the instrument read-out.
Matrix effects are usually compensated by analyzing samples and all calibration standards,
reagent blanks, and quality control (QC) standards in the same matrix Matrix effects may be tested
by serial dilutions, spiked additions, and comparison with an alternative method of analysis. When
the matrix effects are significant and cannot be readily corrected, the analyses must be performed
by standard additions (see appendices C and 0).
12.1.3 Safety
Wear protective clothing (laboratory coat and gloves) and safety glasses when preparing
reagents, especially when concentrated acids and bases are used. The use of concentrated acids
and hydroxide solutions should be restricted to a fume hood. Many metal salts are extremely toxic
and may be fatal if swallowed. Wash hands thoroughly after handling.
Follow the safety precautions of the manufacturer when operating instruments. Gas cylinders
should always be chained or bolted in an upright position.
12.2 Sample Collection, Preservation, and Storage
This procedure uses the soil saturation aliquots prepared as described in Section 11 (see
specifically, sections 11.2 and 11.6.2).
12.3 Equipment and Supplies
12.3.1 Equipment Specifications
12.3.1.1 Determination by Atomic Absorption—
1. Spectrophotometer, with grating monochromator, photomultiplier detector, adjustable slits,
and a wavelength range of 190 to 800 nm.
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2. Burner, as recommended by the instrument manufacturer. When nitrous oxide is used as
the oxidant, a nitrous oxide burner is required.
3. Hollow cathode lamps, single element lamps preferred; multielement lamps may be used.
Electrodeless discharge lamps may be used where available.
4. Balance, capable of weighing to 0.1 g.
5. Balance calibration weights, 3-5 weights covering expected range.
12.3.1.2 Determination by Inductively Coupled Plasma-
1. Inductively Coupled Plasma-Atomic Emission Spectrometer.
2. Balance, capable of weighing to 0.001 g.
3. Balance calibration weights, 3-5 weights covering expected range.
12.3.1.3 Determination by Emission Spectroscopy-
1. Emission spectrometer, direct-reading or internal-standard type; or an atomic absorption
spectrometer operated in the flame emission mode.
2. Balance, capable of weighing to 0.001 g.
3. Balance calibration weights, 3-5 weights covering expected range.
12.3.2 Reagents and Consumable Materials
Acids used in the preparation of standards and for sample processing must be ultra-high
purity grade (e.g., Baker Ultrex grade or SeaStart Ultrapure grade). To minimize concentration of
cations in standard solutions by evaporation, store solutions in linear or high density polyethylene
bottles. Use small containers to reduce the amount of dry element that may be picked up from the
bottle walls when the solution is poured.
Deionized (01) water used for preparing or diluting reagents, standards, and samples must
meet purity specifications for Type I reagent water as given in ASTM D 1193 (ASTM, 1984).
12.3.2.1 Determination by Atomic Absorption-
1. Hydrochloric acid, concentrated (12 M HCI)--Ultrapure grade, Baker Instra-Analyzed or
equivalent.
2. HCI (1 percent v/v)-Add 5 mL concentrated HCI to 495 ml deionized (DI) water.
3. Nitric acid, concentrated-Ultrapure grade, Baker Instra-Analyzed or equivalent.
4. Nitric acid (0.5 percent v/v HNO^-Add 0.50 mL HNO3 to 50 mL DI water and dilute to 100
mL
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5. Primary standard solutions-Prepare from ultra-high purity grade chemicals as directed in
the individual procedures. Commercially available stock standard solutions may also be
used.
6. Dilute calibration standards-Prepare a series of standards of the cation by dilution of the
appropriate stock metal solution in the specific matrix to cover the concentration range
desired. Prepare all calibration standards in concentration units of mg/L.
7. Fuel-Commercial grade acetylene with in-line filter is generally acceptable.
8. Oxidant-Air may be supplied from a compressed-air line, a laboratory compressor, or
from a cylinder of compressed air. Nitrous oxide is supplied from a cylinder of
compressed gas.
9. Lanthanum chloride (LaCy matrix modifier solution-Dissolve 29 g La2O3> slowly and in
small portions, in 250 mL concentrated HCI.
Caution: Reaction is violent. Dilute to 500 mL with DI water.
10. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
11. Weighing pans, disposable.
12. Forms-Form 8 calcium in ammonium acetate, Form 9 magnesium in ammonium acetate,
Form 10 potassium in ammonium acetate, Form 11 sodium in ammonium acetate, Form
QC-8, Form QC-9, Form QC-10, and Form QC-11 (Appendix B, figures B-27 through B-34,
respectively).
12.3.2.2 Determination by Inductively Coupled Plasma-
1. Hydrochloric acid, concentrated (12 M HCI. specific gravity 1.19)-Ultrapure grade, Baker
Instra-Analyzed or equivalent.
2. Hydrochloric acid (50 percent v/v)~Add 500 mL concentrated HCI to 400 mL DI water and
dilute to 1.00 L with DI water.
3. Nitric acid, concentrated (specific gravity 1.41)-Ultrapure grade, Baker Instra-Analyzed or
equivalent.
4. Nitric acid (50 percent v/v)-Add 500 mL concentrated HNO3 to 400 mL DI water and dilute
to 1 L.
5. Primary standard solutions-May be purchased or prepared from ultra-high purity grade
chemicals or metals. All salts must be dried for one hour at 105 *C unless otherwise
specified.
6. Argon, oxygen-free.
7. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
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8. Weighing pans, disposable.
9. Forms-Form 8 calcium in ammonium acetate, Form 9 magnesium in ammonium acetate,
Form 11 sodium in ammonium acetate, Form QC-8, Form QC-9, and Form QC-11 (Appendix
B, figures B-27, B-28, B-30, B-31, B-32, and B-34, respectively).
12.3.2.3 Determination by Emission Spectroscopy-
1. Standard lithium solution-Use either lithium chloride (LiCI) or lithium nitrate (LiNOg) to
prepare standard lithium solution containing 1,000 mg Li/L
Dry LiCI overnight in an oven at 105 *C. Rapidly weigh 6.109 g LiCI and dissolve in 1.0 N
NH4OAc, as needed to match the sample extract matrix Dilute to 1,000 mL with the same
1.0 N NH4OAc solution.
Dry LiNO3 overnight in an oven at 105 "C. Rapidly weigh 9.935 g LiNO3 and dissolve in 1.0
N NH4OAc, as needed to match the sample extract matrix. Dilute to 1,000 mL with the
same 1.0 N NH4OAc solution.
Prepare a new calibration curve whenever the standard lithium solution is changed. Do
not change solutions within a batch.
NOTE: Lithium is used to suppress ionization of K+ and Na+.
2. Primary standard solutions-May be purchased or prepared from ultra-high purity grade
chemicals or metals. All salts must be dried for one hour at 105 *C unless otherwise
specified.
3. Acetylene (commercial grade or better).
4. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
5. Weighing pans, disposable.
6. Forms-Form 10 potassium in ammonium acetate, Form 11 sodium in ammonium acetate,
Form QC-10, and Form QC-11 (Appendix B, figures B-29, B-30, B-33, and B-34,
respectively).
12.4 Calibration and Standardization
Within each class of instruments (AA, ICP, and ES), the calibration procedure varies slightly.
Calibrate by analyzing a calibration blank and a series of at least three standards within the linear
range. If an ICP is used, a multielement standard may be prepared and analyzed. For AA and ES
determinations, the instrument must be calibrated for each analyte by using a separate stan-dard.
The concentration of standards should bracket the expected sample concentration; however, the
linear range of the instrument should not be exceeded. Details of calibration are discussed in
appendices C, D, and E for AA, ICP, and ES, respectively.
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12.5 Quality Control
Log all quality control (QC) data on forms QC-8, QC-9, QC-10, and QC-11 (Appendix B, figures
B-31 through B-34); refer to Section 3.0 for additional information regarding these internal quality
control checks.
Calibration B/anks~Ca\\bra\\or\ blanks for each cation should be analyzed before the initial
sample analysis, at specified intervals thereafter (e.g., after every ten samples) and after the last
sample of each batch. If any blank is higher than the contract-required detection limit (CRDL) listed
in Table 3-2, check the system and reanalyze all samples since the last acceptable calibration blank.
Reagent Blanks-Three reagent blanks, carried through the extraction procedure, are analyzed
with each batch of samples for each cation. The concentration of each blank should be less than
or equal to the CRDL outlined in Table 3-2.
Rep/tcates-One sample from each batch should be extracted and analyzed in duplicate. The
percent relative standard deviation (%RSD) should meet the limits in Table 3-3.
QC Standards-One detection limit quality control check standard (DL-QCCS) should be
analyzed for each cation with each batch of samples. The known concentrations in the DL-QCCS
samples should be about 0.20 mg of each of the cations per liter of 1.0 N NH4OAc. Measured values
should be within 20 percent of known values of the DL-QCCS standards.
QCCSs of concentrations at about mid-calibration range of the samples being analyzed should
be measured for each cation before the first sample, at specified intervals thereafter, e.g. (every
tenth sample) and after the last sample of each batch of samples for both exchanges. Measured
values for each QCCS should be within 10 percent of the known value.
Matrix Spike-Pot each batch of soils, a matrix spike is made to the exchange solution for each
parameter analyzed in the sample. The known spike value should be 1.5 to 3.0 times the measured
concentration, or ten times the CRDL, whichever is greater. Calculated recovery of the spike should
be 90 to 110 percent of the known concentration of the spike.
QC Audit Sample (QCASJ-The QCAS should fall within the accuracy windows provided by the
quality assurance (QA) manager.
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12.6 Procedure
Before proceeding with the analytical procedure, the analyst should be certain that all QC
procedures have been implemented, all lab ware has been properly cleaned, and valid instrumental
detection limits (IDLs) have been obtained, as outlined in Section 3.0 and Appendix A.
General procedures for AA, ICP, and ES are given in sections 12.6.1, 12.6.2, and 12.6.3,
respectively. Detailed procedures are provided in appendices C, D, and E.
NOTE: Figures within the square brackets, [ ], represent the form number and column in
which the data are entered.
12.6.1 Procedure for Determinations by Atomic Absorption
Differences among AA spectrophotometers prevent the formulation of detailed instructions
applicable to every instrument. The analyst should follow the operating instructions for the
particular instrument. In general, after choosing the proper hollow cathode lamp for the analysis,
allow the lamp to warm up for a minimum of 15 minutes unless the instrument is operated in a
double-beam mode. During this period, align the instrument, position the monochromator at the
correct wavelength, select the proper monochromator slit width, and adjust the hollow cathode
current according to the recommendation of the manufacturer. Subsequently, light the flame and
regulate the flow of fuel and oxidant, adjust the burner and nebulizer flow rate for maximum percent
absorption and stability, and balance the photometer. Run a series of standards of the analyte and
calibrate the instrument. Aspirate the samples and determine the concentrations either directly (if
the instrument reads directly in concentration units) or from a calibration curve.
12.6.1.1 Calcium and Magnesium--
1. To each 10.0-mL volume of calibration standard, blank, and sample (soil extract), add
1.00 ml LaCI3 solution. Dilute with DI water to 20 ml_.
2. Calibrate the instrument.
3. Analyze the samples.
NOTE: Initial readout should be made on the 1:1 soil extract:DI water dilution before
any additional dilutions are made. For further dilutions, use a 1:1
water-extraction solution (i.e., 50 percent extracting solution) as the dilution
agent.
4. Dilute and reanalyze any samples for which the concentration exceeds the linear range,
as outlined in Step 1. Record aliquot and diluted volumes: Ca2+, [8-D], [8-E]; Mg2+ [9-D],
[9-E].
5. Record results as mg/L in the diluted solution: Ca2+ [8-FJ; Mg2+ [9-FJ.
12.6.1.2 Potassium and Sodium--
1. Calibrate the instrument.
2. Analyze the samples.
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NOTE: Initial readout should be made on the 1:1 soil extract:DI water dilution before
any additional dilutions are made. For further dilutions, use a 1:1
waterextraction solution (i.e., 50 percent extracting solution) as the dilution
agent.
3. Dilute and reanalyze any sample for which the concentration exceeds the calibrated
range and record aliquot and diluted volumes for K+ [10-D], [10-E]; for Na+ [11-D], [11-E].
NOTE: Record "1.0" in columns D and E for all samples in which no dilutions were
required.
4. Record results as mg/L in the soil extract; if the aliquot was diluted, record the diluted
volume: K+, [10-F]; Na+, [11-FJ.
12.6.2 Procedure for Determinations by Inductively Coupled Plasma
1. Set up the instrument as recommended by the manufacturer. The instrument must be
allowed to become thermally stable before analysis begins (10 to 30 minutes).
2. Profile and calibrate the instrument according to the recommended procedures of the
manufacturer. Flush the system with the calibration blank between each standard.
3. Begin sample analysis, flushing the system with the calibration blank solution between
each sample.
4. Dilute with 1:1 extractDI water solution and reanalyze any samples for which the
concentration exceeds the calibration range, and report aliquot and diluted volumes; Ca2+
[8-D], [8-EJ; Mg2+ [9-D], [9-E]; Na+ [11-D], [11-E].
5. Record results for Ca2+ [8-F], Mg24 [9-F], and Na+ [11-F] and analyze K+ by AA or ES.
12.6.3 Procedure for Determinations by Emission Spectroscopy
NOTE: Locate instrument in an area away from direct sunlight or in an area free of
drafts, dust, and tobacco smoke. Guard against contamination from corks,
filter paper or pulp, perspiration, soap, cleansers, cleaning mixtures, and
inadequately rinsed apparatus. Follow recommendation of the manufacturer
for selecting proper photocell and wavelength, for adjusting slit width and
sensitivity, for appropriate fuel and oxidant pressures, and for the steps
required for warm-up, correcting for interferences and flame background,
rinsing of burner, igniting sample, and measuring emission intensity.
1. Calibrate the instrument.
2. Analyze the samples.
3. Dilute with 1:1 soil extract:DI water solution and reanalyze any samples for which the
concentration exceeds the calibration range and report aliquot and diluted volumes: K+,
[10-D] and [10-E]; Na+, [11-D] and [11-E].
4. Record results for K+ [10-F] and Na+ [11-F] and analyze Ca2+ and Mg2+ by AA or ICP.
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12.7 Calculations
NOTE: Designations within the square brackets, [ ], represent the form number and column
in which the data are entered on forms 8, 9,10,11, and 1 (Appendix B, figures B-27,
B-28, B-29, B-30, and B-9).
Recovered Extract Volume = (Final Weight - Tare Weight) + Density (weight data from Section
11.6.2, Step 3).
Final Extract Vol. [8-C], [9-C], [10-C], or [11-C] = (Final Wt. (g) - Tare Wt. (g)) + 1.0124
Exch. Cation (meq/100 g) = {[inst. reading] x ([total diluted vol.] + [aliq. vol.]) x [final
extract vol.] x 1 L + 1000 mL x 100 x meq + at. wt. (mg) x 1} +
{[sample wt.] x (1 - [MOIST]) + (100 + [MOIST])}
CA OAC [8-G] = {[8-F] x ([8-E] -s- [8-D]) X [8-C] x 0.1 x 0.0499 X 1} -!- {[8-B] x (1 -
[1-D]) + (100 + [1-D])}
MG OAC [9-G] = {[9-F] x ([9-E] + [9-D]) x [9-C] x 0.1 x 0.0822 x 1} + {[9-B] x (1 -
[1-D]) + (100 + [1-D])}
K OAC [10-G] = {[10-F] x ([10-E] -i- [10-D]) x [10-C] x 0.1 x 0.0255 x 1} + {[10-B]
x (1 - [1-D]) + (100 + [1-D])}
NA OAC [11-G] = {[11-F] x ([11-E] -!- [11-D]) x [11-C] x 0.1 x 0.0435 x 1} + {[11-B] x
(1 - [1-D]) + (100 + [1-D])}
12.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specification for Reagent Water, D1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
Fassel, V. A. 1982. Analytical Spectroscopy with Inductively Coupled Plasmas - Present Status and
Future Prospects. In: Recent Advances in Analytical Spectroscopy. Pergamon Press, New
York, New York.
U.S. Environmental Protection Agency. 1983 (revised). Methods for Chemical Analysis of Water and
Wastes, Method 200.0, Atomic Absorption Methods; and Method 200.7, Inductively Coupled
Plasma-Atomic Emission Spectrometric Method for the Trace Element Analysis of Water and
Wastes. EPA 600/4-79/020. U.S. Environmental Protection Agency, Cincinnati, Ohio.
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13.0 Exchangeable Cations in Ammonium Chloride
13.1 Overview
The exchangeable cations (Ca2+, Mg2+, K+, Na+, and AI3+) obtained in unbuffered 1.0 N NH4CI
represent the effective exchange that occurs at field pH. Values of the exchangeable cations
determined by this procedure are theoretically equal to those determined by the buffered NH4OAc
exchange (Section 12.0). The concentrations (meq/100 g) of the exchangeable cations plus acidity
should approximate the cation exchange capacity (CEC) (Section 11.0).
Base saturation is given as the total amount of exchangeable base cations (Ca2+, Mg2+, K+,
and Na+) divided by the CEC. Exchangeable acidity is a measure of the amount of exchangeable
acidic cations on the soil cation exchange complex.
13.1.1 Summary of Method
Previously prepared extracts from the CEC procedure (Section 11.0) are analyzed for aluminum,
calcium, magnesium, potassium, and sodium. Once the concentration of each cation in the soil
extract is determined, the cation concentrations in the original soil sample may be calculated.
Atomic absorption spectroscopy (AA) can be used to measure calcium, magnesium,
potassium, and sodium. A light beam from a hollow cathode lamp, whose cathode is made of the
element to be determined, is directed through the flame into a monochromator and onto a detector
that measures the amount of light passing through the flame. Absorption depends upon the
presence of free, unexcited, ground state atoms in the flame. Since the wavelength of the light
beam is characteristic only of the cation being determined, the light energy absorbed by the flame
is a measure of the concentration of that cation in the extract. A complete discussion of AA
methods is provided in Appendix C.
Inductively coupled plasma spectroscopy (ICP) must be used to measure aluminum and can
be used to measure calcium, magnesium, and sodium. Samples are nebulized to produce an
aerosol. The aerosol is transported by an argon carrier stream to an inductively coupled argon
plasma, which is produced by a radio frequency generator. In the plasma (which is at a
temperature of 6,000 to 10,000 *K) the analytes in the aerosol are atomized, ionized, and ionic
emission spectra is produced. The spectra from all analytes are dispersed by a grating
spectrometer and the intensities of the lines are monitored by photomultiplier tubes. The
photocurrents from the photomultiplier tubes are processed by a computer system. The signal is
proportional to the analyte concentration and is calibrated by analyzing a series of standards (U.S.
EPA, 1983; Fassel, 1982). A thorough discussion of ICP methods is provided in Appendix D.
Emission spectroscopy (ES) can be used to measure potassium and sodium. The sample is
aspirated into a gas flame and excitation is carried out under carefully controlled and reproducible
conditions. The desired spectral line is isolated by the use of interference filters or by a suitable
slit arrangement in light-dispersing devices such as prisms or gratings. The intensity of light is
measured by a phototube potentiometer or other appropriate circuit. The intensity of light at the
appropriate wavelength (e.g., 589 nm for Na+) is approximately proportional to the concentration of
the element. A discussion of ES methods is provided in Appendix E.
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13.1.2 Interferences
No interferences are known for the extraction and acid titration, but several interferences may
occur during analysis of the exchangeable cations, including spectral, chemical, physical, and matrix
effects. Additional details of these interferences and means for their obviation, elimination, or
compensation are provided in appendices C, D, and E.
Spectral interferences are generally caused by spectral overlap from another element or
background contributions. These interferences can usually be corrected by monitoring and
compensating for the effect of interfering elements, selecting another wavelength, correcting
background effects, or using a narrower slit width.
Chemical interferences are often caused by the cations forming molecular compounds instead
of dissociated ions. This interference, most pronounced with the multivalent ions (such as Ca2+,
Mg2+, and especially At34), is negligible with the ICP technique. This interference is often corrected
by the addition of lanthanum or lithium or by the avoidance of anions such as sulfate and
phosphate.
The most common physical interference in the analysis of soils exchange solutions is salt
build-up clogging the burner or nebulizer. Although dilution will reduce this problem, it will also
change the matrix and any effect it may have on the instrument read-out.
Matrix effects are usually compensated for by analyzing samples and all calibration standards,
reagent blanks, and quality control (QC) standards in the same matrix Matrix effects may be tested
by serial dilutions, spiked additions, and comparison with an alternative method of analysis. When
the matrix effects are significant and cannot be readily corrected, the analyses must be performed
by standard additions (see appendices C and D).
13.1.3 Safety
Wear protective clothing (laboratory coat and gloves) and safety glasses when preparing
reagents, especially when concentrated acids and bases are used. The use of concentrated acids
and hydroxide solutions should be restricted to a fume hood. Many metal salts are extremely toxic
and may be fatal if swallowed. Wash hands thoroughly after handling.
Follow the safety precautions of the manufacturer when operating instruments. Gas cylinders
should always be chained or bolted in an upright position.
13.2 Sample Collection, Preservation, and Storage
This procedure uses the soil saturation aliquots prepared as described in Section 11 (see
specifically, sections 11.2 and 11.6.2).
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13.3 Equipment and Supplies
13.3.1 Equipment Specifications
13.3.1.1 Determination by Atomic Absorption-
1. Spectrophotometer, with grating monochromator.photomultiplier detector, adjustable slits,
and a wavelength range of 190 to 800 nm.
2. Burner, as recommended by the instrument manufacturer. When nitrous oxide is used as
the oxidant, a nitrous oxide burner is required.
3. Hollow cathode lamps, single element lamps preferred; multielement lamps may be used.
Electrodeless discharge lamps may be used where available.
4. Balance, capable of weighing to 0.1 g.
5. Balance calibration weights, 3-5 weights covering expected range.
13.3.1.2 Determination by Inductively Coupled Plasma--
1. Inductively Coupled Plasma-Atomic Emission Spectrometer.
2. Balance, capable of weight to 0.01 g.
3. Balance calibration weights, 3-5 weights covering expected range.
13.3.1.3 Determination by Emission Spectroscopy-
1. Flame photometer, direct-reading or internal-standard type; or an atomic absorption
spectrometer operated in the flame emission mode.
2. Balance, capable of weighing to 0.001 g.
3. Balance calibration weights, 3-5 weights covering expected range.
13.3.2 Reagents and Consumable Materials
Acids used in the preparation of standards and for sample processing must be of ultra-high
purity grade (e.g., Baker Ultrex grade or SeaStart Ultrapure grade). To minimize concentration of
cations in standard solutions by evaporation, store solutions in linear or high density polyethylene
bottles. Use small containers to reduce the amount of dry element that may be picked up from the
bottle walls when the solution is poured. Shake each container thoroughly before use to redissolve
any accumulated salts from the walls.
Deionized (DI) water used for preparing or diluting reagents, standards, and samples must
meet purity specifications for Type I reagent water as given in ASTM D 1193 (ASTM, 1984).
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13.3.2.1 Determination by Atomic Absorption-
1. Hydrochloric acid, concentrated (12 M HCI)--Ultrapure grade, Baker Instra-Analyzed or
equivalent.
2. HCI (1 percent v/v)--Add 5 ml_ concentrated HCI to 495 ml DI water.
3. Nitric acid, concentrated-Ultrapure grade, Baker Instra-Analyzed or equivalent.
4. Nitric acid (0.5 percent v/v HNOJ-Add 0.50 ml_ HNO3 to 50 ml DI water and dilute to 100
ml.
5. Primary standard solutions-Prepare from ultra-high purity grade chemicals as directed in
the individual procedures. Commercially available stock standard solutions may also be
used.
6. Dilute calibration standards-Prepare a series of standards of the cation by dilution of the
appropriate stock metal solution in the specific matrix to cover the concentration range
desired. Prepare all calibration standards in concentration units of mg/L.
7. Fuel-Commercial grade acetylene with in-line filter is generally acceptable.
8. Oxidant-Air may be supplied from a compressed-air line, a laboratory compressor, or
from a cylinder of compressed air. Nitrous oxide is supplied from a cylinder of
compressed gas.
9. Lanthanum chloride (LaCy matrix modifier solution-Dissolve 29 g La2O3, slowly and in
small portions, in 250 mL of concentrated HCI.
Caution: Reaction is violent. Dilute to 500 mL with DI water.
10. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
11 Weighing pans, disposable.
12. Forms-Form 12, calcium in ammonium chloride, Form 13, magnesium in ammonium
chloride, Form 14, potassium in ammonium chloride, Form 15, sodium in ammonium
chloride, Form QC-12, Form QC-13, Form QC-14, and Form QC-15 (Appendix B, figures B-35
through B-38 and B-40 through B-43. respectively).
13.3.2.2 Determination by Inductively Coupled Plasma-
1. Hydrochloric acid, concentrated (12 M HCI, specific gravity 1.19)-Ultrapure grade, Baker
Instra-Analyzed or equivalent.
2. Hydrochloric acid (50 percent v/v)~Add 500 mL concentrated HCI to 400 mL DI water and
dilute to 1.00 L with DI water.
3. Nitric acid, concentrated (specific gravity 1.41)-Ultrapure grade, Baker Instra-Analyzed or
equivalent.
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4. Nitric acid (50 percent v/v)--Add 500 ml concentrated HNO3 to 400 mL DI water and dilute
to1 L
5. Primary standard solutions-May be purchased or prepared from ultra-high purity grade
chemicals or metals. All salts must be dried for one hour at 105 *C unless otherwise
specified.
6. Argon, oxygen-free.
7. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
8. Weighing pans, disposable.
9. Forms-Form 12, calcium in ammonium chloride, Form 13, magnesium in ammonium
chloride, Form 15, sodium in ammonium chloride, Form 16, aluminum in ammonium
chloride, Form QC-12, Form QC-13, Form QC-15, and Form QC-16 (Appendix B, figures B-
35, B-36, B-38 through B-41, B-43, and B-44, respectively).
13.3.2.3 Determination by Emission Spectroscopy-
1. Standard lithium solution-Use either lithium chloride (LiCI) or lithium nitrate (LiNOj) to
prepare standard lithium solution containing 1,000 mg Li/L.
NOTE: Lithium is used to suppress ionization of K+ and Na*.
Dry LiCI overnight in an oven at 105 *C. Rapidly weigh 6.109 g LiCI and dissolve in 1.0 N
NH4OAc, as needed to match the sample extract matrix Dilute to 1,000 mL with the same
1.0 N NH4OAc solution.
Dry LiNO3 overnight in an oven at 105 *C. Rapidly weigh 9.935 g LiNO3 and dissolve in 1.0
N NH4OAc, as needed to match the sample extract matrix Dilute to 1,000 mL with the
same 1.0 N NH4OAc solution.
Prepare a new calibration curve whenever the standard lithium solution is changed. Do
not change solutions within a batch.
2. Primary standard solutions-May be purchased or prepared from ultra-high purity grade
chemicals or metals. All salts must be dried for one hour at 105 *C unless otherwise
specified.
3. Acetylene (commercial grade or better).
4. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
5. Weighing pans, disposable.
6. Forms-Form 14, potassium in ammonium chloride, Form 15, sodium in ammonium
chloride, Form QC-14, and Form QC-15 (Appendix B, figures B-37, B-38, B-42, and B-43,
respectively).
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13.4 Calibration and Standardization
Within each class of instruments (AA, ICP, and ES), the calibration procedure varies slightly.
Calibrate by analyzing a calibration blank and a series of at least three standards within the linear
range. If an ICP is used, a multielement standard may be prepared and analyzed. For AA and ES
determinations, the instrument must be calibrated for each analyte by using a separate stan-dard.
The concentration of standards should bracket the expected sample concentration; however, the
linear range of the instrument should not be exceeded. Details of calibration are discussed in
appendices C, D, and E for AA, ICP, and ES, respectively.
13.5 Quality Control
Log all quality control (QC) data on forms QC-12, QC-13. QC-14, QC-15, and QC-16 (Appendix
B, figures B-40 through B-44); refer to Section 3 for additional information regarding these internal
quality control checks.
Calibration 5/a/7/te--Calibration blanks for each cation should be analyzed before the initial
sample analysis, at specified intervals thereafter (e.g., after every ten samples) and after the last
sample of each batch. The calculated concentrations for each blank should be less than 0.10 mg/L
for AI3+ and less than 0.05 mg/L for the other exchangeable cations. If any blank is higher than
these limits, check the system and reanalyze all samples since the last acceptable calibration blank.
Reagent Blanks-Three reagent blanks, carried through the extraction procedure, are analyzed
with each batch of samples for each cation. The concentration of each blank should be less than
or equal to the contract-required detection limit (CRDL) listed in Table 3-2.
Rep/icates-One sample from each batch should be extracted and analyzed in duplicate. The
percent relative standard deviation (%RSD) should meet the limits outlined in Table 3-3.
QC Standards-One detection limit quality control check standard (DL-QCCS) should be
analyzed for each cation with each batch of samples. The concentration of this DL-QCCS should
be about 0.30 mg/L for AI3+ and 0.15 mg/L for other exchangeable cations. Measured values should
be within 20 percent of the known value of the DL-QCCS standards.
QCCSs of concentrations at about mid-calibration range of the samples being analyzed should
be measured for each cation before the first sample, at specified intervals thereafter (e.g., every
tenth sample) and after the last sample of each batch of samples for both exchanges. Measured
values for each QCCS should be within 10 percent of the known value.
Matrix Spike-tor each batch of soils, a matrix spike is made to the exchange solution for each
parameter analyzed in the sample. The known spike value should be 1.5 to 3.0 times the measured
concentration, or ten times the CRDL, whichever is greater. Calculated recovery of the spike should
be 90 to 110 percent of the known concentration of the spike.
QC Audit Sample (QCASj~~n\e QCAS should fall within the accuracy windows provided by the
quality assurance (QA) manager.
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13.6 Procedure
Before proceeding with the analytical procedure, the analyst should be certain that all QC
procedures have been implemented, all labware has been cleaned properly, and valid instrumental
detection limits (IDLs) have been obtained as outlined in Section 3.0 and Appendix A.
General procedures for AA, ICP, and ES are given in sections 13.6.1, 13.6.2, and 13.6.3,
respectively. Detailed procedures are provided in appendices C, D, and E.
NOTE: Figures within the square brackets, [ ], represent the form number and column in
which the data are entered.
13.6.1 Procedure for Determinations by Atomic Absorption
NOTE: AAcan be used to determine all exchangeable cations with the exception of aluminum,
which must be done on ICP.
Differences among AA spectrophotometers prevent the formulation of detailed instructions
applicable to every instrument. The analyst should follow the operating instructions for his particular
instrument. In general, after choosing the proper hollow cathode lamp for the analysis, allow the
lamp to warm up for a minimum of 15 minutes unless the instrument is operated in a double-beam
mode. During this period, align the instrument, position the monochromator at the correct
wavelength, select the proper monochromator slit width, and adjust the hollow cathode current
according to the recommendation of the manufacturer. Subsequently, light the flame and regulate
the flow of fuel and oxidant, adjust the burner and nebulizer flow rate for maximum percent
absorption and stability, and balance the photometer. Run a series of standards of the analyte and
calibrate the instrument. Aspirate the samples and determine the concentrations either directly (if
the instrument reads directly in concentration units) or from a calibration curve.
13.6.1.1 Calcium and Magnesium-
1. Add 1.0 ml of LaCI3 solution to a 10-mL volume of each calibration standard, blank, and
sample. Dilute with DI water to 20 ml. Record the final extract solution volume: Ca2+
[12-CJ; Mg2+ [13-C].
2. Calibrate the instrument.
3. Analyze the samples.
NOTE: Initial readout should be made on the 1:1 soil extract:DI water dilution before any
additional dilutions are made. For further dilutions, use a 1:1 DI waterextraction
solution (i.e., 50 percent extracting solution) as the dilution agent.
4. Dilute and reanalyze any samples for which the concentration exceeds the linear range,
as outlined in Step 1. Record aliquot and diluted volumes: Ca2+, [12-D], [12-E]; Mg2+,
[13-D], [13-E].
5. Record results as mg/L in the soil extract: Ca2+ [12-FJ; Mg2+ [13-FJ.
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13.6.1.2 Potassium and Sodium-
1. Calibrate the instrument.
2. Analyze the samples.
NOTE: Initial readout should be made on the 1:1 soil extract:DI water dilution before any
additional dilutions are made. For further dilutions, use a 1:1 DI water.extraction
solution (i.e., 50 percent extracting solution) as the dilution agent.
3. Dilute and reanalyze any sample for which the concentration exceeds the calibrated range,
and record aliquot and diluted volumes; K+ [14-D]; [14-E]; Na+, [15-D], [15-E].
4. Record results as mg/L in the soil extract: K+ [14-F]; Na+ [15-F].
13.6.2 Procedure for Determinations by Inductively Coupled Plasma
1. Set up the instrument as recommended by the manufacturer. The instrument must be
allowed to become thermally stable before analysis begins (10 to 30 minutes).
2. Profile and calibrate the instrument according to the recommended procedures of the
manufacturer. Flush the system with the calibration blank between each standard.
3. Begin sample analysis, flushing the system with the calibration blank solution between
each sample.
4. Dilute with 1:1 extract:DI water solution and reanalyze any samples for which the
concentration exceeds the calibration range, and report aliquot and diluted volumes; Ca2+
[12-D], [12-E]; Mg2+ [13-D], [13-E]; Na+, [15-D], [15-E]; AI3+, [16-D], [16-E].
5. Record results for Caa+, [12-F]; Mga+ [13-F]; Na+ [15-F]; and AI3+ [16-F]. Analyze K+ by AA
orES.
13.6.3 Procedure for Determinations by Emission Spectroscopy
NOTE: Locate instrument in an area away from direct sunlight and in an area free of
drafts, dust, and tobacco smoke. Guard against contamination from corks, filter
paper or pulp, perspiration, soap, cleansers, cleaning mixtures, and inadequately
rinsed apparatus. Because of differences among instruments, it is impossible to
formulate detailed operating instructions. Follow recommendations of the
manufacturer for selecting proper photocell and wavelength, for adjusting slit
width and sensitivity, for appropriate fuel and oxidant pressures, and for the
steps for warm-up, correcting for interferences and flame background, rinsing of
burner, igniting sample, and measuring emission intensity.
1. Calibrate the instrument.
2. Analyze the samples.
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3. Dilute with 1:1 extract:DI water solution and reanalyze any samples for which the
concentration exceeds the calibration range and record aliquot and diluted volumes: K+
[14-D] and [14-E]; Na+ [15-D] and [15-E].
4. Record results for K+ [14-F] and Na* [15-F]. Analyze Ca2+ and Mg2+ by ICP or AA and AI3+
by ICP.
13.7 Calculations
NOTE: Designations within the square brackets, [ ], represent the form number and
column in which the data are entered on forms 12, 13, 14, 15, 16, and 1
(Appendix B, Figures B-35, B-36, B-37, B-38, B-39, and B-9).
Recovered Extract Volume = (Final weight - Tare weight) + Density (data from Section 11.6.2,
Step 3.)
Final Extract Volume [12-C], [13-C], [14-C], [15-C], or [16-C] - Final wt. (g) - Tare wt. (g) + 1.0105
Exch. Cation (meq/100 g) = {[inst. reading] x ([total dil. vol.] + [aliq. vol.]) x [final extract vol.]
x 1L + 1000 mL x 100 x meq + at. wt. (mg) x 1} + {[sample wt.]
x (1 - [Moist]) + (100 + [Moist])}
CA CL [12-GJ = {[12-F] x ([12-E] + [12-D]) x [12-C] x 0.1 x 0.0499 x 1} + {[12-B]
x (1 - [1-D]) + (100 + [1-D])}
MG CL [13-G] = {[13-F] X ([13-E] + [13-D]) x [13-C] x 0.1 x 0.0822 x 1} + {[13-B]
x (1 - [1-D]) + (100 + [1-D])}
K CL (14-G] = {[14-F] X ([14-E] + [14-D]) X [14-C] x 0.1 X 0.0255 X 1} + {[14-B]
x (1 - [1-D]) + (100 + [1-D])}
NA CL [15-G] = {[15-F] x ([15-E] + [15-D]) x [15-C] x 0.1 x 0.0435 x 1} + {[15-B]
x (1 - [1-D]) + (100 + [1-D])}
AL CL [16-G] = {[16-F] x ([16-E] + [16-D]) x [16-C] x 0.1 x 0.1112 x 1} + {[16-B] X
(1 - [1-D]) + (100 + [1-D])}
13.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specification for Reagent Water, D1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
Fassel, V. A. 1982. Analytical Spectroscopy with Inductively Coupled Plasma Present Status and
Future Prospects. In: Recent Advances in Analytical Spectroscopy. Pergamon Press, New
York, New York.
U.S. Environmental Protection Agency. 1983. Methods for Chemical Analysis of Water and Wastes,
Method 200.0, Atomic Absorption Methods; and Method 200.7, Inductively Coupled Plasma-
Atomic Emission Spectrometric Method for the Trace Element Analysis of Water and Wastes.
EPA/600/4-79/020. U.S. Environmental Protection Agency, Cincinnati, Ohio.
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14.0 Exchangeable Cations in Calcium Chloride
for Lime and Aluminum Potential
14.1 Overview
Lime and aluminum potential are related to the concentrations of calcium (Ca2+) and aluminum
(AI3+), respectively, that are extracted from a soil sample by a dilute calcium chloride (CaCI2)
solution. Lime potential is defined as pH - 1/2 pCa. The p-function is defined as the negative
logarithm (base 10) of the molar concentration of that species, or: pX = -log [X]. The advantage
of using the p-function is that concentration information is available in terms of small positive
numbers. Aluminum potential, KA, is defined as: KA = 3pH - pAI.
The pH value determined in this method should be between the two pH values determined for
each soil sample (see Section 10.0). Extractable Mg2+, K+, and Na+ are also determined for
comparison to amounts determined in the cation exchange capacity (CEC) extracts (see sections
12.0 and 13.0). Fe3+ and AI3+ are determined for comparison to amounts obtained by the extractable
iron and aluminum procedures in Section 16.0.
14.1.1 Summary of Method
The procedure involves extraction of soil with 0.002 M CaCI2. The soil-to-solution ratio is 1:2
for mineral soils and 1:10 for organic soils. The pH is determined using a pH meter and a
combination electrode (see Section 10.0).
Atomic absorption spectroscopy (AA) can be used to measure calcium, magnesium,
potassium, and sodium. A light beam from a hollow cathode lamp, the cathode of which is made
of the element to be determined, is directed through the flame into a monochromator and onto a
detector that measures the amount of light passing through the flame. Absorption depends upon
the presence of free, unexcited, ground state atoms in the flame. Since the wavelength of the light
beam is characteristic only of the cation being determined, the light energy absorbed by the flame
is a measure of the concentration of that cation in the extract. A complete discussion of AA
methods is provided in Appendix C.
Inductively coupled plasma spectroscopy (ICP) may be used to determine calcium, magnesium,
sodium, iron, and aluminum. Samples are nebulized to produce an aerosol. The aerosol is
transported by an argon carrier stream to an inductively coupled argon plasma, which is produced
by a radio frequency generator. In the plasma (which is at a temperature of 6,000 to 10,000 *K) the
analytes in the aerosol are atomized, ionized, and ionic emission spectra is produced. The spectra
from all analytes are dispersed by a grating spectrometer and the intensities of the lines are
monitored by photomultiplier tubes. The photocurrents from the photomultiplier tubes are processed
by a computer system. The signal is proportional to the analyte concentration and is calibrated by
analyzing a series of standards (U.S. Environmental Protection Agency [USEPA], 1983; Fassel, 1982).
A thorough discussion of ICP methods is provided in Appendix D.
Emission spectroscopy (ES) can be used to measure potassium and sodium. The sample is
aspirated into a gas flame and excitation is carried out under carefully controlled and reproducible
conditions. The desired spectral line is isolated by the use of interference filters or by a suitable
slit arrangement in light-dispersing devices such as prisms or gratings. The intensity of light is
measured by a phototube potentiometer or other appropriate circuit. The intensity of light at the
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appropriate wavelength (e.g., 589 nm for Na+) is approximately proportional to the concentration of
the element. A discussion of ES methods is provided in Appendix E.
14.1.2 Interferences
Chemical and spectral interferences can contribute to inaccuracies in analyses of the extracts
by AA, ICP, or ES. Analyses by ICP and ES are subject to physical interferences as well. Additional
details of these interferences and means for their Deviation, elimination, or compensation are
provided in appendices C, D, and E.
Spectral interferences are generally caused by spectral overlap from another element or
background contributions. These interferences can usually be corrected by monitoring and
compensating for the effect of interfering elements, selecting another wavelength, correcting
background effects, or using a narrower slit width.
Chemical interferences are often caused by the cations forming molecular compounds instead
of dissociated ions. This interference, most pronounced with the multivalent ions (such as Ca2+,
Mg2+, and especially AI3+), is negligible with the ICP technique. This interference is often corrected
by the addition of lanthanum or lithium or by the avoidance of anions such as sulfate and
phosphate.
The most common physical interference in the analysis of soils exchange solutions is salt
build-up clogging the burner or nebulizer. Although dilution will reduce this problem, it will also
change the matrix and any effect it may have on the instrument read-out.
Matrix effects are usually compensated by analyzing samples, and all calibration standards,
reagent blanks, and quality control (QC) standards in the same matrix Matrix effects may be tested
by serial dilutions, spiked additions, and comparison with an alternative method of analysis. When
the matrix effects are significant and cannot be readily corrected, the analyses must be performed
by standard additions (see appendices C and D).
Soils high in salts, especially sodium, may interfere with the pH reading and the electrode
response time. Clay particles may clog the liquid junction of the pH reference electrode, slowing the
electrode response time; thoroughly rinse the electrode with deionized (DI) water between sample
readings to avoid this problem. Wiping the electrode dry with cloth, laboratory tissue, or similar
materials or removing the electrode from solution when the meter is not on standby may cause
electrode polarization.
The initial pH of a nonalkaline soil will usually be as much as 0.5 pH unit greater than the pH
taken after the sample has set for 30 minutes or longer. The pH can vary as much as 1.0 pH unit
between the supernatant and soil sediment. Always place the electrode junction at the same
distance (approximately 3 mm) above the surface of the soil sediment to maintain uniformity in pH
readings.
14.1.3 Safety
Wear protective clothing (laboratory coat and gloves) and safety glasses when preparing
reagents, especially when concentrated acids and bases are used. The use of concentrated acids
should be restricted to a fume hood. Many metal salts are extremely toxic and may be fatal if
swallowed. Wash hands thoroughly after handling.
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Follow the safety precautions of the manufacturer when operating instruments. Gas cylinders
should always be chained or bolted in an upright position.
14.2 Sample Collection, Preservation, and Storage
A subsample is taken from the bulk soil sample after it has been air dried, homogenized, and
tested for moisture content (see sections 4.0 and 8.0). Samples should be stored at 4 *C until ready
for analysis. Preparation of the extraction aliquot is described in Section 14.6.1.
14.3 Equipment and Supplies
14.3.1 Equipment Specifications
1. Atomic absorption spectrophotometer, single- or dual-channel, single or double-beam, with
grating monochromator, photomultiplier detector, adjustable slits, wavelength range of 190
to 800 nm, with a strip chart recorder and burner, as recommended by the instrument
manufacturer (for certain elements, nitrous oxide burner required; hollow cathode lamps,
single element lamps preferred, but multielement lamps acceptable; electrodeless
discharge lamps may be used also).
2. Inductively coupled plasma atomic emission spectrometer, computer-controlled, with
background correction capability.
3. Emission spectrometer, either direct-reading or internal-standard type; or atomic
absorption spectrometer in flame emission mode.
4. Digital pH/ millivolt (mV) meter, capable of measuring pH to ±0.01 pH unit and potential
to ±1 mVand temperature to ±0.5 *C. The meter must also have automatic temperature
compensation capability (Orion Model 611 or equivalent).
5. A combination pH electrode, made of high quality, low-sodium glass. At least two
electrodes, one a backup, should be available. Geltype reference electrodes must not be
used; an Orion Ross combination pH electrode or equivalent with a retractable sleeve is
recommended.
14.3.2 Apparatus
1. Shaker.
2. Centrifuge.
3. Balance, capable of weighing to 0.01 g.
4. Glass stirring rods.
5. Volumetric pipets, volumes as needed.
6. Volumetric flasks, volumes as needed.
7. Balance calibration weights, 3-5 weights covering expected range.
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14.3.3 Reagents and Consumable Materials
1. Stock calcium chloride solution (1.0 M CaCI2)~Dissolve 55.49 g anhydrous reagent grade
CaCI2 or 73.51 g CaCI2«2H2O in 01 water and dilute to 500 ml.
2. Calcium chloride (CaCI2) 0.002 M--Dilute 4 mL 1.0 M CaCI2 to 2.0 L with DI water. If the
pH of this solution is not between 5 and 6.5, adjust the pH by addition of dilute HCI or
saturated Ca(OH)2.
3. Calibration standards (Ca2+, Mg2+, K4, Na+, Al34, and Fe34).
4. pH calibration buffers (pH 4.0,7.0, and 10.0)~Commercially available pH calibration buffers
(National Bureau of Standards [NBS]-traceable) at pH values of 4.0 and 7.0 (two sets
from different sources for calibration and quality control checks).
5. Potassium chloride (3M)-Dissolve 224 g KCI in DI water and dilute to 1 L.
6. Potassium chloride (0.1 M).
7. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
8. Bottles, linear polyethylene (LPE), with cap: 25-mL for mineral soil; 50-mL for organic soil.
9. Tubes, glass, 25-mL, centrifuge or culture, with caps.
10. Filter, membrane, 0.45-/jm pore.
11. Weighing pans, disposable.
12. Forms-Form 18, pH in 0.002 M calcium chloride, Form 19, calcium in 0.002 M calcium
chloride, Form 20, magnesium in 0.002 M calcium chloride, Form 21, potassium in 0.002
M calcium chloride. Form 22, sodium in 0.002 M calcium chloride, Form 23, iron in 0.002
M calcium chloride, Form 24, aluminum in 0.002 M calcium chloride, Form QC-18, Form QC-
19, Form QC-20, Form QC-21, Form QC-22, Form QC-23, and Form QC-24 (Appendix B,
figures B-45 through B-58, respectively).
14.4 Calibration and Standardization
Within each class of instruments (AA, ICP, and ES), the calibration procedure varies slightly.
Curves must be linear and cover the range of concentrations measured in the extract. Calibration
standards for Ca24 determinations are prepared using DI water, while calibration standards for
Mg2+, Na4, K4, Al34, and Fe34 are prepared in the 0.002 M CaCI2 solution. Detailed calibration
procedures for AA, ICP, and ES are provided in appendices C, D, and E, respectively; pH meter
calibration is detailed in Section 10.0, and calibration of balances is described in Appendix A.
14.5 Quality Control
Log all QC data on forms QC-18 through QC-24 (Appendix B, figures B-52 through B-58,
respectively); refer to Section 3.0 for additional information concerning these internal quality control
checks.
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Calibration fl/a/?Ars--Calibration blanks for each cation should be analyzed before the initial
sample analysis, at specified intervals thereafter (e.g., after every ten samples) and after the last
sample of each batch. For Mg2+, K+, and Na+, the calibration blank prepared (0.002 M CaCI2
solution) should be 0.05 mg/L or less. For Ca2+, the calibration blank (DI water) should be 0.500
mg/L or less. For the Fe3* and AI3+ cations, blanks (0.002 M CaCI2 solution) should be 0.10 mg/L or
less. If any blank is higher than these limits, check the system and reanalyze all samples since the
last acceptable calibration blank.
Reagent fi/a/7/rs-Three reagent blanks are analyzed with each batch of samples for each
cation. Reagent blanks consist of the 0.002 M CaCI2 extraction solution passed through the
analytical procedure without any soil being present. The reagent blank for Ca24 should be between
76 and 84 mg/L. The pH blank should be between 4.5 and 7.5 pH units. Each of the other reagent
blanks should be less than or equal to the contract-required detection limit (CRDL) in Table 3-2.
Rep//cates~One sample from each batch should be extracted and analyzed in duplicate for all
six cations. Triplicate analyses of the duplicate sample for each batch is required for pH. The
percent relative standard deviation (%RSD) should meet the limits outlined in Table 3-3.
QC Standards-One detection limit quality control check standard (OL-QCCS) should be
analyzed for each cation with each batch of samples. The DL-QCCS standard is prepared in 0.002
M CaCI2. Recommended concentration of Mg2+, K+, and Na+ in the DL-QCCS is 0.15 mg/L each;
concentration of Ca2+ is 0.50 mg/L; concentration of Fe3+ and AI3+ is 1.0 mg/L each. Measured
values for Ca2* should be 76 to 84 mg/L; measured values for each of the other cations should be
within 20 percent of the known concentration.
QCCSs of concentrations at about mid-calibration range of the samples being analyzed should
be measured for each cation before the first sample, at specified intervals thereafter (e.g., every
tenth sample) and after the last sample of each batch of samples for both exchanges. Measured
values for each QCCS should be within 10 percent of the known value.
A pH 4.00 standard, from a different preparation source or lot number than that used for the
calibration, is used as the QCCS for pH. Each reading for the pH QCCS should fall between 3.95
and 4.05 pH units.
Spike Solution-Pot each batch of samples, a spike solution should be analyzed three times
for Ca2* content. The spike solution consists of the 0.002 M CaCL extraction solution that is used
for the extraction of all six cations. Measured values for the Ca2 in the spike solution should be
76 to 84 mg/L Ca2+.
Matrix Spike-Pot each batch of soils, the extract from one sample is spiked with a known
concentration for each cation being determined. The known spike value should be 1.5 to 3.0 times
the measured concentration, or ten times the CRDL, whichever is greater. Calculated recovery of
the spike should be 90 to 110 percent of the known concentration of the spike. No spike is required
for the pH determination.
QC Audit Sample (QCAS}-~tt\e QCAS should fall within the accuracy windows provided by the
QA manager.
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14.6 Procedure
Before proceeding with the analytical procedure, the analyst should be certain that all QC
procedures have been implemented, all labware has been properly cleaned, and valid instrumental
detection limits (IDLs) have been obtained, as outlined in Section 3.0 and Appendix A. Detailed
procedures for AA, ICP, and ES are provided in appendices C, D, and E.
NOTE: Figures within the square brackets, [ ], represent the form number and column in
which the data are entered.
14.6.1 Extraction
1. For mineral soils, weigh 20.00 g air-dry soil to nearest 0.01 g, and for organic soils, weigh
8.00 g air-dry soil to nearest 0.01 g. Record: pH [18-B]; Ca2+ [19-B]; Mg2+ [20-C]; K+ [21-
CJ; Na+ [22-C]; Fe3+ [23-C]; and Al34 [24-B].
2. Place weighed samples in sample tube and add 40.0 ml of 0.002 M CaCI2 to mineral soils
and 80.0 mL of 0.002 M CaCI2 to the organic soils. Record: pH [18-C]; Ca2+ [19-C]; Mg2+
[20-C]; K+ [21-CJ; Na+ [22-C]; Fe3+ [23-C]; and AJ3+ [24-C].
3. Stir each sample thoroughly to assure it is completely wetted with the 0.002 M CaCI2
extract solution.
4. Securely cap the sample tubes, place the closed sample tubes securely in a horizontal
position on a mechanical shaker and shake for at least one hour, let stand overnight, and
resuspend prior to centrifugation.
5. Decant about half the liquid into a 50-mL centrifuge tube, saving the remainder of the
liquid and wet soil for the pH determination.
6. Centrifuge the samples in the sample tubes for 5 minutes.
7. Filter the supernatant using a 0.45-pm filter into a clean sample tube and refrigerate at
4 *C until analyses are made for Ca2+, Mg2+. K+, Na+, Fe3+, and AI3+.
14.6.2 Cation Determination
1. Determine the concentration of the six cations using appropriate instrumentation:
M - Ca2+, Mg2+, K+, and Na+
ICP - Ca2+, Mg2+, Na+, Fe3+, and AI3+
ES - K+ and Na+
2. Dilute any sample with high concentration for the respective analyte measured above the
linear dynamic calibration range of the instrument.
NOTE: When analyzing for Mg2+, K+, Na+, Fe3+, and Al34, a maximum dilution of 1:1 (one
part extractions part DI water) is permissible prior to preliminary analysis.
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3. Log the aliquot volume, diluted volume, and measured diluted concentration (mg/L) for the
six cations: Ca2+ [19-D], [19-E], M9-F]; Mg2+ [20-D], [20-E], [20-F]; K+ [21-D], [21-E], [21-F];
Na+ [22-D], [22-E], [22-F]; Fev [23-D], [23-E], [23-F]; and AI3+ [24-D], [24-E], [24-F].
14.6.3 pH Determination
1. Allow the suspension to settle for at least 1 minute. Immerse the pH electrode into the
suspension so that the reference junction is below the surface of the solution, but above
the sediment.
2. Read the pH to the nearest 0.01 pH unit and record: [19-D],
3. After measurements are completed, store the electrode in 0.1 M KCI storage solution. Do
not let the sensing element and reference junction dry out. The level of the storage
solution should be one inch below the filling solution level to prevent influx of the storage
solution. Check periodically that the electrode reservoir is full of filling solution.
14.7 Calculations
NOTE: No calculations are required in order to obtain pH values; the final value is [18-D].
Designations within the square brackets, [ ], represent the form number and column
in which the data are entered on forms 19, 20, 21, 22, 23, 24, and 1 (Appendix B,
figures B-46, B-47, B-48, B-49, B-50, B-51, and B-9).
Cations (meq/100 g) = {[inst. reading] x ([total dil. vol.] + [aliq. vol.]) x [final extract vol.] x
1L + 1000 mL x 100 g x (meq + at. wt. (mg)) x 1} + {[sample wt.j x
(1 - [Moist]) + (100 + [Moist])}
CA.CL2 [19-G] = {[19-F] X ([19-E] + [19-D]) x [19-C] X 0.1 X 0.0499 x 1} + {[19-B] X
(1 - [1-D]) + (100 + [1-D])}
MG CL2 [20-G] = {[20-F] x ([20-E] -t- [20-D]) x [20-C] x 0.1 x 0.0823 x 1} + {[20-B] x
(1 - [1-D]) + (100 + [1-D])}
K CL2 [21-G] = {[21-F] x ([21-E] -*- [21-D]) x [21-C] x 0.1 x 0.0252 X 1} + {[21-B] X
(1 - [1-D]) + (100 + [1-D])}
NA CL2 [22-G] - {[22-F] x ([22-E] -t- [22-D]) x [22-C] x 0.1 x 0.0435 x 1} -s- {[22-B] x
(1 - [1-D]) + (100 + [1-D])}
FE CL2 [23-G] = {[23-F] x ([23-E] + [23-D]) x [23-C] x 0.1 x 0.0537 x 1} + {[23-B] X
(1 - [1-D]) + (100 + [1-D])}
AL CL2 [24-G] = {[24-F] x ([24-E] -s- [24-D]) X [24-C] x 0.1 x 0.1112 x 1} + {[24-B] x
(1 - [1-D]) + (100 + [1-D])}
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14.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.10,
Standard Specification for Reagent Water, D-1193-77 (reapproved 1983). American Society for
Testing and Materials, Philadelphia, Pennsylvania.
Fassel, V. A. 1982. Analytical Spectroscopy with Inductively Coupled Plasma Present Status and
Future Prospects. Jn: Recent Advances in Analytical Spectroscopy. Pergamon Press, New
York, New York.
U.S. Environmental Protection Agency. 1983 (revised). Methods for Chemical Analysis of Water and
Wastes. Method 200.0, Atomic Absorption Methods, and Method 200.7, Inductively Coupled
Plasma Atomic Emission Spectrometric Method for the Trace Element Analysis of Water and
Wastes. EPA-600/4-79/020. U.S. Environmental Protection Agency, Cincinnati, Ohio.
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15.0 Exchangeable Acidity
15.1 Overview
Exchangeable acidity is a fairly arbitrary quantity composed of four types of acidity:
1) H+ derived from hydrolysis of AI3+,
2) hydrolysis of nonexchangeable Al,
3) weakly acidic groups predominantly on organic matter, and
4) exchangeable H.
The method most frequently used to determine exchangeable acidity involves treatment of the
soil sample with a barium chloride triethanolamine (BaCI2-TEA) solution buffered to pH 8.2 followed
by titration of the extracted solution. This method measures total potential acidity (Thomas, 1982).
15.1.1 Summary of Method
Exchangeable acidic ions are extracted from a soil sample using a mechanical extractor with
a BaCI2-TEA extracting solution. The excess reagent in the extract is back-titrated with HCI. Results
are expressed as milliequivalents (meq) exchangeable acidity per 100 g soil.
15.1.2 Interferences
Atmospheric carbon dioxide can interfere with the BaCI2-TEA extraction. The use of buffered
solution is meant to minimize this effect. Use of automated equipment minimizes the effects of
variation in technique.
15.1.3 Safety
Wear protective clothing (laboratory coat and gloves) and safety glasses when preparing
reagents, especially when concentrated acids and bases are used. The use of concentrated acids
and ammonium hydroxide solutions should be restricted to a fume hood.
Follow the safety precautions of the manufacturer when operating the instruments.
15.2 Sample Collection, Preservation, and Storage
A subsample is taken from the bulk soil sample after it has been air dried, homogenized, and
tested for moisture content (see sections 4.0 and 8.0). Samples should be stored at 4 *C until ready
for analysis. Preparation of the soil extractions is described in sections 15.6.1 and 15.6.2.
15.3 Equipment and Supplies
15.3.1 Apparatus and Equipment
1. Balance, capable of weighing to 0.01 g.
2. Mechanical extractor, 24-place, manufactured by Centurion, Inc. or equivalent (see
Figure 11-1).
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3. Pipettors, volume adjustable to 25 ml (2 required).
4. Erlenmeyer flasks, 250-mL and 125-mL
5. Reciprocating shaker.
6. Volumetric flasks, volumes as needed.
7. Automatic titrator.
8. Digital pH/ millivolt (mV) meter, capable of measuring pH to ±0.01 pH unit and potential
to ±1 mV and temperature to ±0.5 *C. The meter must also have automatic temperature
compensation capability (Orion Model 611 or equivalent).
9. A combination pH electrode, made of high quality, low-sodium glass. At least two
electrodes, one as a backup, should be available. Gel-type reference electrodes must not
be used; an Orion Ross combination pH electrode or equivalent with a retractable sleeve
is recommended.
10. Balance calibration weights, 3-5 weights covering expected range.
15.3.2 Reagents
1. Buffer solution for mineral soils [0.5 N BaCI2-0.10 N N(CH2CH2OH).j]--Dissolve 61.07 g
BaCI2»2H2O and 14.92 g TEA in CO2-free, deionized (DI) water and dilute to 1.00 L. Adjust
pH to 8.2 with 10 percent HCI. Protect solution from C02 contamination by attaching a
drying tube containing Ascarite to the air intake of the storage vessel.
2. Buffer solution for organic soils [0.5 N BaCI2-0.2 N N(CH2CH2OH).J~Dissolve 61.07 g
BaCI2-2H2O and 29.8 g TEA in CO2-free, DI water and dilute to 1.00 L Adjust pH to 8.2
with 10 percent HCI. Protect solution from CO2 contamination by attaching a drying tube
containing Ascarite to the air intake of the storage vessel.
3. Replacement solution (0.5 N with respect to BaCI2)~Dissolve 61.07 g BaCI2»2H2O with 5
mL of the appropriate BaCI2-TEA buffer solution and dilute to 1.00 L with DI water.
4. Hydrochloric acid, concentrated (12 M HCI)--Ultrapure, Baker Instra-Analyzed or equivalent.
5. Hydrochloric acid (1 percent v/v)~Add 5 mL concentrated HCI to 495 mL DI water.
6. Hydrochloric acid (0.100 N, standardized)-Dilute 8.32 mL concentrated HCI to 1.00 L with
DI water. Standardize against reagent grade sodium carbonate to methyl orange
endpoint. This may also be purchased as certified, standardized 0.100 N HCI.
7. Hydrochloric acid (0.050 N, standardized)-Dilute 4.15 mL concentrated HCI to 1.00 L with
DI water. Standardize against reagent grade sodium carbonate to methyl orange
endpoint. This may also be purchased as certified, standardized 0.050 N HCI.
8. pH calibration buffers (pH 4.0,7.0, and 10.0)--Commercially available pH calibration buffers
(National Bureau of Standards [NBS]-traceable) at pH values of 4.0, 7.0, and 10.0 (two
sets from different sources for calibration and quality control checks).
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9. Washed analytical filter pulp, Schleicher and Schuell, No. 289 (see Section 11.6.1 for
washing procedure). Commercial pulps are often contaminated and will have to be
washed.
10. Ascarite.
11. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
15.3.3 Consumable Materials
1. Syringes, 60-mL, one sample tube and one extraction syringe per sample.
2. Stirring rods, glass; one per sample.
3. Tubes, glass, 25-mL, centrifuge or culture, with caps.
4. Bottles, polyethylene, 25-mL, optional.
5. Weighing pans, disposable.
6. Forms-Form 17, barium chloride-TEA acidity and Form QC-17 (Appendix B, figures B-59
and B-60).
15.4 Calibration and Standardization
Calibrate the titrator for the volume of solution to be delivered. Calibrate the pH electrode by
using two pH buffers that bracket the desired endpoint (see Section 10.4). Normalities of titrants
(label values) should be checked weekly during use. If the check normality differs from the label
value by more than 5 percent, perform two additional checks. Calculate the mean normality from
the three checks; this mean becomes the label value used in the acidity calculations. The same
standard titrant must be used for the entire batch of samples.
Balance calibration is detailed in Appendix A.
15.5 Quality Control
Log all quality control (QC) data on Form QC-17 (Appendix B, Figure B-60; refer to Section 3.0
for additional information regarding these internal quality control checks.
Calibration £/a/7/rs--Calibration blanks should be analyzed before the initial sample analysis,
at specified intervals thereafter (e.g., after every ten samples) and after the last sample of each
batch. The calibration blank should be composed of 20 ml of the buffer solution, 40 mL of the
replacement solution, and 100 mL of DI water. The calibration blank should contain between 1.3 and
1.8 meq for mineral soils. If any blank is outside these limits, check the system and reanalyze all
samples since the last acceptable calibration blank.
Reagent Blanks-three reagent blanks, carried through the extraction procedure, are analyzed
with each batch of samples. This composition will result in a solution composition of between 1.3
and 1.8 meq for mineral soils. The mean of the reagent blank values is used in the acidity
calculation.
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Replicates--Or\e sample from each batch should be weighed, extracted, and analyzed in
duplicate. The percent relative standard deviation (%RSD) should meet the limits listed in Table 3-3.
QC Standarcfs-One detection limit quality control check standard (DL-QCCS) should be
analyzed with each batch of samples. Measured values should be within 20 percent of the known
value of the DL-QCCS standard.
QCCSs of concentrations at about the mid-calibration range of the samples being analyzed
should be measured before the first sample, at specified intervals thereafter (e.g., every tenth
sample) and after the last sample of each batch. Measured values for each QCCS should be within
10 percent of the known value.
Prepare the DL-QCCS and QCCS as follows: mix 20 mL of the buffer solution, 40 mL of the
replacement solution, and 100 mL of DI water; for the DL-QCCS, add sufficient acid (HCI) to
neutralize approximately 0.015 meq (a suggested addition of 0.3 mL of 0.050 N HCI is appropriate);
for the QCCS, neutralize approximately 20 percent of the buffer to reach the mid-calibration range
(a suggested addition of 8 mL of 0.050 N HCI is appropriate for mineral soils and 8 mL of 0.1 N HCI
is appropriate for organic soils).
QC Audit Sample (QCASJ-The QCAS should fall within the accuracy windows provided by the
quality assurance (QA) manager.
15.6 Procedure
Exchangeable acidity analyses should not be done until the samples are properly prepared,
the air-dry moisture is determined, and valid instrumental detection limits (IDLs) (see sections 3.0,
4.0, and 8.0), are determined. Data should be logged following the procedures described in Section
3.0.
NOTE: Figures within the square brackets, [ ], represent the form number and column in
which the data are entered.
15.6.1 Mineral Soils
1. Tightly compress a 1-g ball of filter pulp into the bottom of a syringe barrel with a
modified plunger. (To modify the plunger, remove the rubber portion and cut off the
plastic protrusion.) Tap the plunger and syringe assembly on a tabletop several times.
2. Weigh 2.00 g air-dry mineral sample into tube and record exact weight [17-B]. Place
sample tube in upper disc of extractor and connect to inverted extraction syringe. The
plunger of this syringe is inserted in the slot of the stationary disc of the extractor.
Attach pinch clamp to delivery tube of syringe barrel. Add 10.00 mL BaCI2-TEA buffer
solution for mineral soils to the sample. Stir the sample mixture with a glass stirring rod
for 10 seconds. Leave stirring rod in syringe. Allow sample to stand for 30 minutes.
3. Set extractor for a 30-minute rate and extract until 0.5 to 1.0 cm of solution remains above
each sample. If necessary, turn off extractor to prevent soil from becoming dry.
4. Add a second 10.00-mL aliquot of BaCI2-TEA buffer solution and continue extracting until
nearly all solution has been pulled through sample. Add replacement solution from
pipettor in two 20-mL aliquots, passing the first aliquot through the sample before adding
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the next. Total time for replacement should be approximately 30 minutes. Quantitatively
transfer extract to an Erlenmeyer flask. Record the total volume of buffer plus replace-
ment solutions [17-C].
NOTE: DI water may be used at this point to aid in the quantitation transfer. The final
volume of DI water should be 100 mL - see Step 5.
5. 77traf/on~Md 100 mL DI water to extract in Erlenmeyer flask. Use an automatic titrator
to titrate with 0.050 N HCI to a 4.60 pH endpoint. Record volume [17-D] and normality [17-
E] of titrant. If the volume of titrant of any sample is less than 5 percent of that
measured for the blank, resolve the problem before further analysis.
15.6.2 Organic Soils
1. Tightly compress a 1-g ball of filter pulp into the bottom of a syringe barrel with a
modified plunger. (To modify the plunger, remove the rubber portion and cut off the
plastic protrusion.) Tap the plunger and syringe assembly on a tabletop several times.
2. Weigh 2.00 g of air-dry organic sample soil into small glass tube and record exact weight
[17-B]. Add 5.00 mL BaCI2-TEA buffer solution for organic soils to the sample, cap, and
shake the tube and contents for 1 hour on a reciprocating shaker. Place sample tube in
upper disc of extractor and connect to inverted extraction syringe, with the syringe plunger
inserted in the slot of the stationary disc of the extractor. Attach pinch clamp to delivery
tube of syringe barrel. Quantitatively transfer contents of small glass tube to sample
tube with 5.00 mL buffer solution.
NOTE 1: Five to 10 mL of buffer solution may be used to transfer soil to syringe - see
Step 4.
NOTE 2: Some organic soils have very high acidity, which may require reducing the
amount of soil to 1.00 g to stay in the mid-range of the titration procedure; note
and flag (see Table 3-4) all data appropriately.
3. Set extractor for a 30-minute rate and extract until 0.5 to 1.0 cm of solution remains above
each sample. If necessary, turn off extractor to prevent soil from becoming dry.
4. Add a second 10.00-mL aliquot of BaCI2-TEA buffer solution and continue extracting until
nearly all solution has been pulled through sample. Add replacement solution from
pipettor in two 20-mL aliquots, passing the first aliquot through the sample before adding
the next. Total time for replacement should be approximately 30 minutes. Quantitatively
transfer extract to an Erlenmeyer flask. Record the total volume of buffer plus replace-
ment solutions [17-C].
NOTE 1: If 10-mL was used in Step 2, then 5 mL must be used here. Total buffer used
must equal 20.00 mL. A second extraction is essential.
NOTE 2: DI water may be used at this point to aid in the quantitative transfer. The final
volume of DI water added must equal 100 mL (see Step 5).
5. 77trat/on~Md 100 mL DI water to extract in Erlenmeyer flask. Use an automatic titrator
to titrate with 0.100 N HCI to a 4.60 pH endpoint. Record volume [17-D] and normality
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[17-E] of titrant. If the volume of titrant of any sample is less than 5 percent of that
measured for the blank, resolve the problem before further analysis.
15.7 Calculations
NOTE: Designations within the square brackets, [ ], represent the form number and column
in which the data are entered on forms 17 and 1 (Appendix B, Figures B-59 and B-1).
Exch. Acidity (meq/100 g) - {([Mean Blank] (ml)] - [Titrant (ml)]) x [Normality of Titrant]
x 1} + {[sample wt.] x (1 - [Moist]) + (100 + [Moist])}
AC BACL [17-F] - {([Mean Blank] - [17-D]) x [17-E] x 1} + {[17-B] x (1 - [1-D])
+ (100 + [1-D])}
15.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specificatton for Reagent Water, D-1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
Thomas, G. W. 1982. Exchangeable cations. IQ: A. L Page, Miller, R. H., Reeney, D. R. (eds.)
Methods of soil analysis. Agronomy 9, Partz. American Society of Agronomy, Madison
Wisconsin.
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16.0 Extract able Iron, Aluminum, and Silicon
16.1 Overview
Iron and aluminum are extracted from soil by sodium pyrophosphate, citrate-dithionite, and
acid-oxalate solutions. According to the Johnson and Todd (1983) iron and aluminum speciation
scheme, the pyrophosphate extract contains organically bound iron and aluminum, the citrate-
dithionite extract contains non-silicate Fe3+ and AI3+, and the acid-oxalate extract contains organic
and amorphous oxides of Fe3+ and AI3+. The exchangeable AI3+ from the unbuffered NH4CI extract
(see Section 13.0) is more indicative of readily available At3* under field conditions. The Fe3+ and
AI3+ values from the pyrophosphate, acid-oxalate, and citrate-dithionite extracts relate directly to the
sulfate adsorption capacity and have been used as an indication of this property (Fernandez, 1983).
Silicon is extracted with the acid oxalate.
16.1.1 Summary of Method
Each of three portions of a soil sample is treated with a different solution to extract iron and
aluminum. The three extracting solutions are 0.1 M sodium pyrophosphate, a sodium citrate-sodium
dithionite solution, and an oxalic acid-ammonium oxalate solution. After extraction, the three
solutions are analyzed for iron, aluminum, and silicon by inductively coupled plasma spectroscopy
(ICP).
In ICP, samples are nebulized to produce an aerosol. The aerosol is transported by an argon
carrier stream to an inductively coupled argon plasma, which is produced by a radio frequency
generator. In the plasma (which is at a temperature of 6,000 to 10,000 *K) the analytes in the
aerosol are atomized, ionized, and ionic emission spectra is produced. The spectra from all analytes
are dispersed by a grating spectrometer, and the intensities of the lines are monitored by photo-
multiplier tubes. The photocurrents from the photomultiplier tubes are processed by a computer
system. The signal is proportional to the analyte concentration and is calibrated by analyzing a
series of standards (U.S. Environmental Protection Agency [USEPA], 1983; Fassel, 1982). A thorough
discussion of ICP methods is provided in Appendix D.
16.1.2 Interferences
Chemical, spectral, and physical interferences can contribute to inaccuracies in analysis of the
extracts by ICP. Additional details of these interferences and means for their obviation, elimination,
or compensation are provided in Appendix D.
Spectral interferences are generally caused by spectral overlap from another element or
background contributions. These interferences can usually be corrected by monitoring and
compensating for the effect of interfering elements, selecting another wavelength, correcting
background effects, or using a narrower slit width.
Chemical interferences are often caused by the cations forming molecular compounds instead
of dissociated ions. This interference, most pronounced with the multivalent ions (such as Al3+), is
negligible with the ICP technique. This interference is often corrected by the addition of lanthanum
or lithium or by the avoidance of anions such as sulfate and phosphate.
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The most common physical interference in the analysis of soils exchange solutions is salt
build-up clogging the burner or nebulizer. Although dilution will reduce this problem, it will also
change the matrix and any effect it may have on the instrument read-out.
Matrix effects are usually compensated for by analyzing samples, and all calibration standards,
reagent blanks, and quality control (QC) standards in the same matrix Matrix effects may be tested
by serial dilutions, spiked additions, and comparison with an alternative method of analysis. When
the matrix effects are significant and cannot be readily corrected, the analyses must be performed
by standard additions (see appendices C and D).
16.1.3 Safety
Wear protective clothing (laboratory coat and gloves) and safety glasses when preparing
reagents, especially when concentrated acids and bases are used. The use of concentrated acids
and hydroxide solutions should be restricted to a fume hood.
Follow the safety precautions provided by the manufacturer when operating instruments. Gas
cylinders should be chained or bolted in an upright position.
16.2 Sample Collection, Preservation, and Storage
A subsample is taken from the bulk soil sample after it has been air dried, homogenized, and
tested for moisture content (see sections 4.0 and 8.0). Samples should be stored at 4 *C until ready
for analysis. Preparation of the soil extractions is described in sections 16.6.1, 16.6.2, and 16.6.3.
NOTE: The subsample may be ground to pass a No. 60 (U.S. No.) or No. 100 sieve, if desired.
16.3 Equipment and Supplies
16.3.1 Equipment Specifications
1. Inductively coupled plasma atomic emission spectrometer, computer-controlled, with
background correction capability.
2. Digital pH/millivolt (mV) meter, capable of measuring pH to ±0.01 pH unit, potential to ±1
mv, and temperature to ±0.5 *C. The meter must also have automatic temperature
compensation capability (Orion Model 611 or equivalent).
3. A combination pH electrode, made of high quality, low-sodium glass. At least two
electrodes, one as a backup, should be available. Gel-type reference electrodes must not
be used; an Orion Ross combination pH electrode or equivalent with a retractable sleeve
is recommended.
16.3.2 Apparatus
1. Balance, capable of weighing to nearest 0.01 g.
2. Reciprocating box shaker.
3. Centrifuge.
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4. Repipet or equivalent.
5. Fleakers, or equivalent glassware.
6. Volumetric pipets, volumes as needed.
7. Volumetric flasks, volumes as needed.
8. Balance calibration weights, 3-5 weights covering expected range.
9. Cardboard box, large enough to hold 250-mL bottle.
16.3.3 Reagents
16.3.3.1 Sodium Pyrophosphate Extraction--
1. National Bureau of Standards [NBS]-traceable pH buffers of pH = 7 and pH = 10.
2. Sodium pyrophosphate (Na4P2O7»10H2O), 0.1 M-Dissolve 446.1 g Na4P2O7«10 H2O in
deionized (DI) water. Dilute to 10 L Adjust to pH 10.0 by dropwise additions of 1 N
NaOH or 1 N H3PO<.
3. Sodium hydroxide (NaOH), 1 N-Dissolve 10 g NaOH in DI water. Dilute to 250 ml. Store
in polyethylene container.
4. Phosphoric acid (H3POJ, concentrated.
5. Superfloc 16, 0.2 percent solution (v/v) in DI water (possible source: American Cyanamid
Co., P.O. Box 32787, Charlotte, NC 28232; telephone: (800) 438-5615).
6. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
16.3.3.2 Citrate-Dithionite Extraction--
1. Sodium dithionite (Na2S2OJ.
2. Sodium citrate (Na3CeH5Oj,-5H2O).
3. Citrate-dithionite reagent-Dissolve 160 g sodium dithionite and 2,000 g sodium citrate into
approximately 8 L of DI water. Dilute to 10 L. Store at 4 *C and use the same day.
NOTE: This may require prolonged magnetic stirring or additional DI water to totally
dissolve the salts.
4. Superfloc 16, 0.2 percent solution (v/v) in DI water.
5. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
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16.3.3.3 Acid-Oxalate Extractlon-
1. NBS-traceabte pH buffers of pH - 4 and pH - 3 or pH - 2.
2. Ammonium oxalate [(NH4)2C204*H2O].
3. Oxalic acid (H2C204»H20).
4. Acid-oxalate reagent-Solution A: Dissolve 284 g ammonium oxalate [(NH4)2C204*H20] in
DI water and dilute to 10 L Solution B: Dissolve 252 g oxalic acid (H2C204*H20) in Dl
water and dilute to 10 L. Mix four parts Solution A with three parts Solution B. Adjust pH
to 3.0 by adding either Solution A or B.
5. Superfloc 16, 0.2 percent.
6. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
16.3.4 Consumable Materials
1. Centrifuge bottles, 250-mL, polypropylene.
2. Bottles, linear polyethylene (LPE), 25-mL
3. ICP vials, provided by ICP manufacterer or clean 250-mL LPE bottles.
4. Weighing pans, disposable.
5. Forms-Form 25, pyrophosphate extractable iron, Form 26, pyrophosphate extractable
aluminum, Form 27, acid oxalate extractable iron, Form 28, acid oxalate extractable
aluminum, Form 29, acid oxalate extractable silicon, Form 30, citrate dithionite extractable
iron, Form 31, citrate dithionite extractable aluminum, and forms QC-25 through QC-31
(Appendix B, figures B-61 through B-74).
6. Aluminum foil, heavy duty.
16.4 Calibration and Standardization
The matrix of the calibration standards should match the matrix of the soil extracts as closely
as possible to assure maximum accuracy. Therefore, // is highly recommended that the calibration
standards be prepared with the extracting solution rather than water as the diluent.
Calibrate the instrument by analyzing a calibration blank and a series of at least three
standards within the linear range. A multielement standard may be prepared and analyzed. The
concentration of standards must bracket the expected sample concentration; however, the linear
range of the instrument should not be exceeded.
Detailed procedures for ICP calibration are given in Appendix D; pH meter calibration is
discussed in Section 10.4; and calibration of balances is discussed in Appendix A.
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16.5 Quality Control
Log all QC data on forms QC-25 through QC-31 (Appendix B, figures B-68 through B-74); refer
to Section 3.0 for additional information concerning these internal quality control checks.
Calibration 5/a/7Ars~Calibration blanks for both Fe3+ and AJ3+ in the three extracts should be
analyzed before the initial sample analysis, at specified intervals thereafter (e.g., after every ten
samples) and after the last sample of each batch. Each blank should have a concentration of 0.50
mg/L or less.
Reagent Blanks-Three reagent blanks, carried through the extraction procedure, are analyzed
with each batch of samples. Each blank should have a concentration of 0.50 mg/L or less.
Replicates-One sample from each batch should be extracted in duplicate for each of the three
extracting solutions and analyzed for Fe3+ and AI3+ in each of the extracts and Si4* in the acid-
oxalate extract. The percent relative standard deviation (% RSO) should meet the limits listed in
Table 3-3.
QC Standards-One detection limit quality control check standard (DL-QCCS) should be
analyzed with each batch of samples for Fe3+ and AI3+ in each of the three extracts and for Si4+ in
acid-oxalate solution. Concentrations of both Fe3+ and Al3* in the three extraction solutions, as well
as for Si4* in acid-oxalate solution, should be within 1.00 to 1.50 mg/L. Measured results for the DL-
QCCS should be within 20 percent of the known concentrations.
QCCSs of concentrations at about mid-calibration range of the samples being analyzed should
be measured for both Fe3+ and AI3+ in each of the three extracts and Si4+ in the acid-oxalate
solution. These measurements should be performed before the first sample, at specified intervals
thereafter (e.g., every tenth sample) and after the last sample of each batch. Measured values for
each QCCS should be within 10 percent of the known value.
Matrix Spike-Por each batch of soils, each extract from one sample should be spiked with a
known concentration for each variable being determined. The concentration of sample plus spike
should be between 1.5 to 3 times the measured concentration of the sample. Calculated recovery
of the spike should be 90 to 110 percent of the known concentration of the spike.
QC Audit Sample (QCAS)~7\\e QCAS should fall within the accuracy windows provided by the
quality assurance (QA) manager.
16.6 Procedure
Before proceeding with the analytical procedure, the analyst should be certain that all QC
procedures have been implemented, all labware has been properly cleaned, and valid instrumental
detection limits (IDLs) have been obtained, as outlined in Section 3.0 and Appendix A, Data should
be logged following the procedures described in Section 3.0. Detailed procedures for ICP are given
in Appendix D.
NOTE: Figures within the square brackets, [ ], represent the form number and column in
which the data are entered.
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16.6.1 Sodium Pyrophosphate Extraction
1. Place 2.00 g of air-dry mineral or organic soil into a 250-mL centrifuge bottle and record
exact weight [25-B] and [26-B]. Add 200 mL 0.1 M Na4P2O7, cap, and shake overnight (16
hours) on a reciprocating box shaker at approximately 1 to 2 cycles per second. The
shaker should be properly ventilated to prevent heat buildup.
2. Remove centrifuge bottle from shaker. Add 4 mL of 0.2 percent Superfloc solution. Shake
for 15 seconds and centrifuge for 10 minutes. Record total volume, 204 mL, used in the
extraction [25-C] and [26-C].
3. Remove centrifuge bottle from centrifuge. Examine the supernatant for suspended clays.
The supernatant may not be clear because the pyrophosphate solution is relatively
viscous and the clays are sodium-saturated. If it is not, repeat Step 2 and the
centrifugation until supernatant is clear.
4. Decant and save the supernatant. Store the supernatant at 4 *C prior to analysis.
5. Analyze for Fe3+ and A13+ by ICP within 24 hours of completion of the extraction. Log the
concentration in mg/L in [25-F] and [26-F].
6. Dilute any sample having a concentration above the linear dynamic calibration range of
the instrument. Log the aliquot volume, diluted volume, and measured concentration in
the diluted volume as follows: Fe3+: [25-D], [25-E], [25-F]; AI3+: [26-D], [26-E], [26-F].
16.6.2 Acid-Oxalate Extraction
This extraction is sensitive to light; therefore, it should be performed under conditions of
darkness. Samples may be protected from light by wrapping bottles in heavy-duty aluminum foil.
1. Weigh 2.00 g of air-dry mineral or organic soil into 250-mL bottles and record exact weight
[27-B], [28-B], and [29-BJ.
2. Add 200 mL of acid-oxalate reagent to the soil samples.
3. Place the 250-mL bottles in a container to protect from light and shake on a reciprocating
box shaker for 4 hours at 1 to 2 cycles per second. Alternately, the reciprocating box
shaker may be located in a light-protected area.
4. Add 4 mL of 0.2 percent Superfloc solution and centrifuge for 10 minutes. Log total
solution, 204 mL, in [27-C], [28-C], and [29-C].
5. Transfer the clear supernatant liquid to vials.
6. Analyze for Fe3+, AI3+, and Si4+ by ICP.
7. Dilute any sample having a concentration above the linear dynamic calibration range of
the instrument.
8. Log aliquot and diluted volume and measured concentration as follows: Fe3+: [27-D], [27-
E], [27-F]; AI3+: [28-D], [28-E], [28-F]; Si4+: [29-D], [29-E], [29-F].
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16.6.3 Citrate-Dithlonite Extraction
1. Weigh approximately 4.00 g air-dry mineral or organic soil into a 250-mL centrifuge bottle
and record exact weight [30-B] and [31-B]. Add 125 ml_ of the citrate-dithionite extraction
solution, cap, and shake overnight (16 hours) on a reciprocating box shaker at 1 to 2
cycles per second.
2. Add 4 mL of 0.2 percent Superfloc solution and shake vigorously for approximately 30
seconds. Centrifuge for 10 minutes (higher speeds and longer times may be required for
soils high in silt and clay). Record total volume, 129 ml, used in the extraction [30-C] and
[31-C].
3. Remove centrifuge bottle from centrifuge. Examine the supernatant for suspended clays.
If the supernatant is not clear, repeat Step 2.
4. Decant and save the supernatant for Fe3+ and AI3+ analysis. Store the supernatant at
4*C.
5. Analyze for Fe3+ and AJ3+ by ICP.
6. Dilute any sample with concentration above the linear dynamic calibration range of the
instrument.
7. Log aliquot volume, diluted volume, and measured concentration as follows: Fe3+: [30-D],
[30-E], [30-FJ; AJ3+: [31-D], [31-E], [31-F].
16.7 Calculations
NOTE: Designations within the square brackets, [ ], represent the form number and column
in which the data are entered on forms 25, 26, 27, 28, 29, 30, 31, and 1 (Appendix B,
figures B-61, B-62, B-63, B-64, B-65, B-66, B-67, and B-9).
Cation (wt%) = {[inst. reading] x ([diluted vol.] + [aliq. vol.]) x [initial
extract vol.] x 1000 mL x 1 g mg x 100 x 1} •+•
{[sample wt.] x (1 - [Moist]) + (100 + [Moist])}
Pyrophosphate Extract: FE PYP [25-G] = {[25-F] x ([25-E] + [25-D]) x [25-C] x 0.0001 x 1} +
{[25-B] x (1 - [1-D]) H- (100 + [1-D])}
AL PYP [26-G] = {[26-F] x ([26-E] -s- [26-D]) x [26-C] x 0.0001 x 1} +
{[26-B] x (1 - [1-D]) + (100 + [1-D])}
Acid-Oxalate Extract: FE AO [27-G] = {[27-F] x ([27-E] + [27-D]) x [27-C] x 0.0001 x 1} +
{[27-B] x (1 - [1-D]) + (100 -I- [1-D])}
AJ AO [28-G] = {[28-F] x ([28-E] -s- [28-D]) x [28-C] x 0.0001 X 1} +
{[28-B] X (1 - [1-D]) -!- (100 + [1-D])}
SI AO [29-G] = {[29-F] x ([29-E] + [29-D]) x [29-C] X 0.0001 X 1} +
{[29-B] x (1 - [1-D]) -!- (100 + [1-D])}
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Citrate Dithionite Extract: FE CD [30-G] = {[30-F] x ([30-E] + [30-D]) x [30-C] x 0.0001 x 1}
{[30-B] x (1 - [1-D]) + (100 + [1-D])}
AL_CD [31-G] = {[31-F] X ([31-E] + [31-D]) x [31-C] x 0.0001 x 1} +
{[31-B] x (1 - [1-D]) + (100 + [1-D])}
16.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specification for Reagent Water, D-1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
Fassel, V. A. 1982. Analytical Spectroscopy with Inductively Coupled Plasmas - Present Status and
Future Prospects. In: Recent Advances in Analytical Spectroscopy Pergamon Press, New
York, New York.
Fernandez, I. 1983. Field Study Program Elements to Assess the Sensitivity of Soils to Acidic
Deposition Induced Alterations in Forest Productivity. Technical Bulletin No. 404. National
Council of the Paper Industry for Air and Stream Improvement, Inc. New York, New York.
Johnson, D. W. and D. E. Todd. 1983. Some Relationships among Fe, Al, C, and SO4 in a Variety
of Forest Soils. Soil Sci. Soc. Am. J., 47:702 -800.
U.S. Environmental Protection Agency. 1983 (revised). Methods for Chemical Analysis of Water and
Wastes. Method 200.0, Atomic Absorption Methods and Method 200.7, Inductively Coupled
Plasma Atomic Emission Spectrometrfc Method for the Trace Element Analysis of Water and
Wastes. EPA/600/4-79/020. U.S. Environmental Protection Agency, Cincinnati, Ohio.
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17.0 Extract able Sulfate
17.1 Overview
Sulfur, in the form of sulfate (SO/*) is the principal anion in acidic deposition in the eastern
U.S. The ability of soils to adsorb sulfate is one of the principal factors affecting the rate and
extent of soil and watershed response to acidic deposition. Quantification of existing pools of
adsorbed sulfate on a soil, concurrent with measurements of sulfate adsorption capacity of that
soil, provide useful information for understanding the status and for predicting the future response
of the soil to acidic deposition.
Sulfate can be adsorbed to soil in several ways, which in turn affect the extent to which that
sulfate can be displaced or exchanged from the soil surface. Sulfate held by electrostatic bonding
is weakly held and can be readily exchanged by other anions. In addition sulfate can be adsorbed
by exchange of one or a pair of ligands (covalent bonds between an oxyanion and metal oxides on
the soil surface). Two extractions have been developed to characterize the amount of sulfate
present on the soil and extent to which it is reversibly sorbed. Water extraction (deionized water)
removes free sulfate salts in the soil (usually present in negligible amounts), sulfate retained on the
soil by electrostatic bonding, and a portion of sulfate retained by ligand exchange; the extent to
which the latter is removed is highly variable and is dependent on the solid-solution phase
partitioning characteristics of the soil. Phosphate (PO,3") extraction, in contrast, is intended to
provide a quantitative extraction of adsorbed sulfate. Phosphate forms stronger ligands with metal
oxide surfaces than does sulfate and is thus preferentially adsorbed, displacing sulfate from
adsorption sites. The relative ligand strengths, along with mass action effects and sequential
extractions in the phosphate technique, should provide nearly quantitative displacement of non-
crystalline, inorganic sulfate from soil surfaces.
17.1.1 Summary of Method
Two aliquots of a soil sample are extracted. Deionized (DI) water is the extracting matrix for
readily available sulfate. The extracting matrix for sulfate that is more difficult to dislocate is 0.016
M sodium phosphate (containing 500 mg P/L). After the extractions are completed, the analytes are
determined by ion chromatography (1C).
17.1.2 Interferences
An interference can occur during the ion chromatographic analysis of the 0.016 M NaH2PO4
extract. At such a high concentration, the phosphate peak overlaps the SO,2" peak under typical 1C
conditions (usually phosphate elutes prior to sulfate). By using the mixed eluent 0.0020 M
Na2CO3/0.0020 M NaOH (an eluent whose pH is greater than the pK of HPO/ [pK = 12.37] and
which is sufficiently buffered to maintain the pH in the presence of the eluting phosphate),
phosphate elutes after SO/", and the interference is minimized or eliminated. Elution time for sulfate
is increased by nearly ten minutes with this modification.
Soil extracts can rapidly degrade a column; therefore, cleaning with dilute acid is recommended
after every 50 samples. Also, the use of guard columns is highly recommended to extend the life
of the separator column and improve analytical reproducibility.
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17.1.3 Safety
Wear protective clothing (laboratory coat and gloves) and safety glasses when preparing
reagents, especially when concentrated acids and bases are used. Follow the safety precautions
of the manufacturer when operating instruments.
17.2 Sample Collection, Preservation, and Storage
A subsample is taken from the bulk soil sample after it has been air dried, homogenized, and
tested for moisture content (see sections 4.0 and 8.0). Samples should be stored at 4 *C until ready
for analysis. Preparation of the soil extractions is described in sections 17.6.1 and 17.6.2.
17.3 Equipment and Supplies
17.3.1 Equipment Specifications
1. Ion chromatograph, Dionex models 10, 12, 14, 16, or 2000 series or equivalent with AS3,
AS4a, or equivalent anion separator column, anion fiber or micromembrane suppressor
column or equivalent; appropriate guard column is required to preserve the separator
column.
2. Automated injection system, commercially available from several manufacturers.
3. Data recording system, integrator or strip chart recorder for recording ion
chromatographs; the nominal output to recorder is 1.0 volts. The Dionex plane parallel
electrode conductivity detector or equivalent unit gives a linear response with
concentration until electronic saturation occurs at approximately 4.0 volts. Therefore,
several analytical ranges on recorders set at different full-scale voltages can be monitored
simultaneously.
17.3.2 Apparatus
1. Balance, capable of weighing to 0.001 g.
2. Centrifuge.
3. Filtration apparatus.
4. Reciprocating shaker.
5. Vortex mixer (optional).
6. Volumetric pipets, volumes as needed.
7. Volumetric flasks, volumes as needed.
8. Balance calibration weights, 3-5 weights covering expected range.
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17.3.3 Reagents
Unless stated otherwise, all chemicals must be American Chemical Society (ACS) Reagent
Grade or better. The concentrated and working eluents, as well as the regenerant used, are based
on the recommendation of the manufacturer for the particular column and instrument used. These
may be altered to increase resolution or decrease separation time. The eluents, suppressors, and
regenerants are presented for a Dionex unit with an AS series anion separator column. These will
change with the manufacturer and column used. All modifications should be documented before
routine analysis begins.
1. Phosphate extract solution (NaH2PO4» H2O), 0.016 M (500 mg P/L)-For extraction of routine
soils; dissolve 22.27 g NaH2PO4»H2O in DI water and dilute to 10.00 L
2. Phosphate standard solution (NaH2PO4» H20), 0.032 M (1,000 mg P/L)~For standards; 4.454
g NaH2PO4-H2O in DI water and dilute to 1.00 L
3. Concentrated eluent, 0.40 M Na2CO3-Dissolve 42.40 g Na2CO3 in DI water and dilute to
1.00 L. Seal and store until use.
4. Sodium hydroxide (50 percent wt/v)--Dissolve 50 g NaOH (pellets or flakes) in DI water
and dilute to 100 ml. This dissolution generates heat; therefore, a water or ice-bath
should be used to cool the dissolution vessel. Alternately, allow solution to stand
overnight to cool. Sodium carbonate may precipitate.
5. Working eluent, 0.0020 M Na2CO.j/0.0020 M NaOH-Dilute 20.0 ml concentrated eluent to
4.00 L and adjust pH to 12.5 with 50 percent NaOH. Other working eluents for the 1C type
columns include: (1) 0.003 M Na2CO3 for water extractable sulfate and 0.002 M
NaHCO3/0.0025 M NaOH for phosphate extractable sulfate, and (2) 0.003 M
NaHCO3/0.0024 M Na2CO3 for both sulfates. The eluent used must give clean separation
of the peaks without excessive band broadening.
6. Sulfuric acid (HjSOJ, 2.5 M--Dilute 34.7 mL concentrated H2SO4 to 1.00 L.
7. Fiber suppressor regenerant-For water-extractable samples, H2SO4 (0.025 M)-Dilute 10
mL of 2.5 M H2SO4 to 1.0 L with DI water. This can be made in large batches and stored
for later use (up to one year).
8. Magnesium sulfate (MgSOJ, anhydrous-Must be dried and desiccated prior to weighing.
9. Stock standard (1,000 mg S/L)-Dissolve 3.75 g MgSO4 in DI water and dilute to 1.00 L.
10. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
17.3.4 Consumable Materials
1. Centrifuge tubes, with screw caps (50-mL centrifuge tubes with screw caps, optional).
2. Membrane filters, 0.45-^m pore; rinsed three times with DI water.
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3. Parafilm.
4. Weighing pans, disposable.
5. Forms-Form 32, water extractable sulfate, Form 33, phosphate extractable sulfate, Form
QC-32, Form QC-33, and 1C Form (Appendix B, figures B-75 through B-79, respectively).
17.4 Calibration and Standardization
17.4.1 Water Extract
Dilute aliquots of the stock standard (Section 17.3.3, Step 9) with DI water to prepare five
calibration standards ranging from 0 to 5 mg S/L. These calibration standards should be prepared
fresh daily. Other concentrations may be used as long as the calibration standards bracket the
sample concentrations. Follow the procedure given in Section 17.6.3.2.
17.4.2 Phosphate Extract
Add 25.0 mL of the phosphate standard solution to 50.0 mL volumetric flasks and aliquots of
the stock standard (Section 17.3.3, Step 9) to prepare five calibration standards ranging from 0 to
10 mg S/L when the mixture is diluted to 50.0 mL with DI water. This results in a series of
calibration standards of 0-10 (mg S/L) in 500 mg P/L. These standards should be prepared fresh
daily. Other concentrations of sulfate (mg S/L) may be used as long as the calibration standards
bracket the sample concentrations. Follow the procedure given in Section 17.6.3.2.
17.5 Quality Control
Log the quality control (QC) data on forms QC-32 and QC-33 (Appendix B, figures B-77 and
B-78); refer to Section 3.0 for additional information concerning these internal quality control checks.
Record 1C resolution test data on Form 1C (Appendix B, Figure B-79).
Calibration £/a/?Ars--Calibration blanks (0.00 mg S/L standard) should be analyzed before the
initial sample analysis, at specified intervals thereafter (e.g., after every ten samples) and after the
last sample of each batch. Measured results for each blank should be 0.025 mg S/L or less. If the
blank is higher than this limit, check the system and reanalyze all samples since the last acceptable
calibration blank.
Reagent B/a/?/rs--Three reagent blanks, carried through the extraction procedure, are analyzed
with each batch of samples. The calculated concentration of each blank should be less than or
equal to the contract-required detection limit (CRDL) listed in Table 3-2.
f?ep//cates~One sample from each batch should be weighed, extracted, and analyzed in
duplicate for each of the two extractable sulfate extracts. The percent relative standard deviation
(%RSD) should meet the limits outlined in Table 3-3.
QC Standards-These standards should be prepared from standards having the same
composition as the stock standard but from a separate source of sulfate. One detection limit
quality control check standard (DL-QCCS) having a known concentration of about 0.10 mg S/L in
each extract should be analyzed with each batch of samples. Measured values should be within
20 percent of the known value.
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QCCSs of concentrations at about mid-calibration range of the samples being analyzed should
be measured before the first sample, at specified intervals thereafter (e.g., every tenth sample) and
after the last sample of each batch of samples for both extracts. Measured values for each QCCS
should be within 10 percent of the known value.
Matrix Spikes-tor each batch of soils, one sample is spiked with a known concentration of
sulfate. The concentration of sample plus spike should be between 1.5 and 3 times the measured
concentration of the sample with no spike. In determining the recovery of the spike, the volume of
the spike is assumed to be negligible. Recovery should be 90 to 110 percent of the spike
concentration.
QC Audit Sample (QCAS^-Ths QCAS should fall within the accuracy windows provided by the
quality assurance (QA) manager.
1C Resolution 7
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17.6.2 Extraction of Sulfate by Sodium Phosphate (NaH2POJ Solution
1. Place 5.00 g of air-dry mineral soil or 2.50 g of air-dry organic soil into a 100-mL centrifuge
tube. If 50-ml centrifuge tubes are used, weigh 2.50 g of air-dry mineral soil or 1.25 g air-
dry organic soil.
2. Add 20 mL 0.016 M NaH2PO4 (500 mg P/L), or 10 mL if 50-mL centrifuge tubes are used.
3. Shake tube on a reciprocating box shaker for 30 minutes at 1 to 2 cycles per second. To
ensure that soil is not accumulating at the base of each centrifuge tube, stop the shaker
after 10 minutes and either invert each tube several times by hand or mix each tube on
a vortex mixer.
4. Centrifuge for 10 minutes. If the supernatant is not clear, repeat centrifugation. When
it is clear, decant supernatant into a clean, 100-mL volumetric flask.
5. Repeat steps 2, 3, and 4 three times. Combine all 4 supernatants and bring to 100.00-mL
volume with phosphate extraction solution (500 mg/L P/L). Log sample weight [33-B] and
final volume [33-C], 100.0 mL (or 50 mL if 2.50 g sample of a mineral soil or 1.25 g of an
organic soil Is used).
6. Filter the diluted extract solution through a 0.45-^m membrane filter.
7. Store the solution at 4 *C and analyze for sulfate by ion chromatography within 24 hours
(see Section 17.6.3).
17.6.3 Determination of Sulfate by Ion Chromatography
This procedure is based on methods employing Dionex ion chromatographs. Other equivalent
systems may be used with modifications to the columns, chromatographic conditions, and reagents.
In these cases, follow the recommendations of the manufacturer. Analyze both the water and
phosphate extracts of the soil samples.
17.6.3.1 Operating Specifications—
The following operating specifications and procedures are recommended for the Dionex-type
system. Other systems require similar procedures.
• Recording system, 10 or 30 pS/cm full scale deflection; 100 ^S/cm for some cases;
linearity should be checked regularly since this may vary and cause error.
• Injection loop, 0.05 or 0.10 mL; 50 /uL may be preferable for some phosphate samples to
reduce pH problems.
• Flow rate, 2.0 to 2.3 mL/min.
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• Pressure gauge or similar device, used as pump-stroke noise suppressor, as required for
unit.
NOTE: Make certain that pressure does not exceed the recommendations of the
manufacturer for the column.
17.6.3.2 Procedure-
1. Operate the fiber or micromembrane suppressor as recommended by the manufacturer.
Generally, the suppressor must be in an upright position with regenerant flowing from
bottom to top.
2. Set up the recorders or integrators for the most sensitive setting for the sample range
being analyzed. Set the second channel for a high range, or perform dilutions when
necessary. Operate integrators according to the instructions of the manufacturer.
3. Pump eluent through the columns. After a stable baseline is obtained, adjust the recorder
zero to approximately 10 percent of the chart. Inject the highest standard. As the highest
standard elutes, adjust the recorder range to approximately 90 percent of the chart.
Repeat several analyses of the highest standard to be certain that the gain is stable and
the peaks are reproducible. Analyze the resolution standard and determine the resolution.
If the phosphate-sulfate resolution does not exceed 60 percent, replace or clean the
separator column and repeat from Step 1.
4. Analyze the standards in random order. Load the injection loop, manually or via the
autosampler, with the standard to be analyzed. Load five to ten times the volume
required to flush the sample loop thoroughly; then inject the standard. Wash injector loop
thoroughly between each sample. For each analysis, measure and record the peak height
either manually or with a data system. If an integrator is available, record the peak area.
5. Repeat Step 4 for analysis of QC samples, matrix spikes, blanks, and soil extracts. If
using an autosampler, fill it with the samples.
6. Dilute and reanalyze each sample for which the concentration exceeds the calibrated
range. Log in data as follows: water extract: aliquot volume [32-D], diluted volume [32-
E], concentration (instrument reading in mg S/L) [32-F]; phosphate extract: aliquot volume
[33-D], diluted volume [33-E], concentration (instrument reading in mg S/L) [33-F].
NOTE: Use 0.16 M phosphate extract solution (17.3.3, Step 1) for phosphate extracts.
17.7 Calculations
NOTE: Designations within the square brackets [ ] represent the form number and column in
which the data are entered on forms 32, 33, and 1 (Appendix B, figures B-75, B-76,
and B-9).
Built-in microprocessors, available with many instruments, provide the most valid results. The
use of these read-outs should be approved by the laboratory or QA manager; otherwise, one of the
alternative techniques should be used:
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From the peak heights, calculate the analyte concentration in the extract as follows:
1. Use a graph-Construct a calibration curve by plotting concentration of standard versus
peak height (or peak area) for each standard. Read the concentration of the analyte
directly from the calibration curve.
2. Use a linear least squares fit.
Extractable Sulfate (mg S/kg) - {[Inst. reading] x ([dilut. vol.] + [aliq. vol.]) x
[Init. extract vol.] x (1 L/1000 ml) x (1000 g / kg) x 1} +
{[sample wt.] x (1 - [MOIST]) + (100 + [MOIST])}
SO4 H2O [32-G] - {[32-F] x ([32-E] + [32-D]) x [32-C] x 1} + {[32-B] x (1 - [1-D]) +
(100 + [1-D])}
S04 PO4 [33-G] = {[33-F] x ([33-E] + [33-D]) x [33-C] x 1} + {[33-B] x
(1 - [1-D]) + (100 + [1-D])}
17.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards Vol. 11.01,
Standard Specification for Reagent Water, D-1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
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18.0 Sulfate Adsorption Isotherms
18.1 Overview
The ability of a soil to adsorb sulfate (SO,2") is one of the principal factors affecting the rate
and extent of soil response to acidic deposition. Sulfate adsorption by a soil will result in a
proportional delay or reduction in cation leaching from the soil, and in soils with high adsorption
capacity can delay the onset of adverse effects on surface waters for several decades. Sulfate (or
other anion) adsorption capacity is related to several other soil variables; adsorption increases with
surface area and Fe2+/AI3+ hydrous oxide content in the soil, varies inversely with soil pH (Tabatabai,
1982) and inversely with soil organic content. The ability of a soil to adsorb SO,2" can be
characterized by development of an adsorption isotherm (i.e., a partitioning function relating
relationships between concentrations of dissolved and adsorbed SO,2" over a useful concentration
range). The procedures described here provide data used to generate such an isotherm for soils,
but do not describe actual generation of an isotherm. Procedures described here measure
net SO,2" retention by soils for a range of SO,2" adsorption corresponding to the equilibrated
concentration of dissolved SO,2" for each slurry, and an isotherm can then be fitted by regression
to the resulting set of data points for each individual soil. (Fernandez, 1983; Johnson and Todd,
1983.)
18.1.1 Scope and Application
Sulfate adsorption isotherms are analyzed only for mineral soils (see Section 7.7 for
determination of mineral and organic soils).
The most direct and effective way to determine sulfate-adsorption capacity utilizes sulfate
adsorption isotherms. In this method, sulfate adsorption isotherms are developed by measuring
the amount of sulfate remaining in solution after contact with a soil sample. These sulfate
adsorption isotherms allow comparisons to be made between horizons or between pedons.
18.1.2 Summary of Method
Six aliquots of the same soil sample are shaken with solution containing 0, 2, 4, 8, 16, and 32
mg sulfur per liter, respectively. The mixtures are centrifuged and filtered, and the resulting filtrate
is analyzed for sulfate by ion chromatography (1C). The difference between the original
concentrations of the sulfur solutions and the final concentrations after this procedure indicates the
sulfur uptake or release by the soil.
18.1.3 Interferences
Soil texture, iron and aluminum content, pH, and organic content of the soil are factors which
affect adsorption capacity; alteration of these properties by sample processing should be avoided.
Calcium, magnesium, or potassium salts may be used; use of sodium salts is not recommended.
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18.1.4 Safety
Wear protective clothing (laboratory coat and gloves) and safety glasses when preparing
reagents, especially when concentrated acids and bases are used. The use of concentrated acids
should be restricted to a fume hood. Follow the safety precautions of the manufacturer when
operating the instruments.
18.2 Sample Collection, Preservation, and Storage
A subsample is taken from the bulk soil sample after it has been air dried, homogenized, and
tested for moisture content (see sections 4.0 and 8.0). Samples should be stored at 4 *C until ready
for analysis. Sample preparation is described in Section 18.6.1.
18.3 Equipment and Supplies
18.3.1 Equipment Specifications
1. Ion chromatograph, Dionex models 10, 12, 14, 16, or 2000 series or equivalent with AS3,
AS4a, or equivalent anion separator column, anion fiber or micromembrane suppressor
column or equivalent; appropriate guard column is required to preserve the separator
column.
2. Automated injection system, commercially available from several manufacturers.
3. Data recording system, integrator or strip chart recorder for recording ion
chromatographs; the nominal output to recorder is 1.0 volts. The Dionex plane parallel
electrode conductivity detector or equivalent unit gives a linear response with
concentration until electronic saturation occurs at approximately 4.0 volts. Therefore,
several analytical ranges on recorders set at different full-scale voltages can be
monitored simultaneously.
18.3.2 Apparatus
1. Balance, capable of weighing to 0.01 g.
2. Volumetric pipet, 50-mL (pipettor, optional).
3. Vortex mixer.
4. Reciprocating shaker.
5. Centrifuge.
6. Membrane filtration apparatus (Luer-Lok, plastic or glass syringes with membrane
filters or equivalent).
7. Balance calibration weights, 3-5 weights covering expected range.
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18.3.3 Reagents and Consumable Materials
1. Primary sulfate SO42" solution (1,000 mg S/L)--Dissolve 3.75 g anhydrous MgSO4 in
deionized (DI) water and dilute to 1.00 L MgSO4 must be dried and desiccated before
weighing for sample preparation.
2. Adsorption solutions-Dilute 2.00, 4.00, 8.00, 16.00, and 32.00 mL of 1,000 mg S/L primary
solution to 1.00 L in separate volumetric flasks. This yields working standards of 2.00,
4.00, 8.00, 16.00, and 32.00 mg S/L, respectively. It is most convenient if 2- to 4-L
batches of adsorption solution can be prepared. Each solution must be within 3
percent of its theoretical concentration (2 percent for the 32.00 mg S/L primary
solution).
3. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
4. Centrifuge tubes, 100-mL, with screw caps (50-mL centrifuge tubes with screw caps,
optional).
5. Membrane filters, 0.45-jum pore size; washed three times with 100 mL of DI water.
6. Weighting pans, disposable.
7. Forms-Form 34, 0 mg S/L isotherm, Form 35, 2 mg S/L isotherm, Form 36, 4 mg S/L
isotherm, Form 37, 8 mg S/L isotherm, Form 38, 16 mg S/L isotherm, Form 39, 32 mg
S/L isotherm, forms QC-34 through QC-39, and Form 1C (Appendix B, figures B-80
through B-91, and Figure B-79 respectively).
18.4 Calibration and Standardization
Calibrate the ion chromatograph as recommended by the manufacturer. Prepare working
standards fresh daily and verify the concentrations by 1C. Analyze adsorption solutions and
report on forms QC-34 through QC-39 (Appendix B, figures B-86 through B-91, respectively). Log
1C resolution test data on Form 1C (Appendix B, Figure B-79). Remake adsorption solutions if the
concentrations are not within 3 percent of the theoretical concentrations (2 percent for the 32 mg
S/L solution). Calibration standards must be from a source independent of the primary sulfate
solution prepared for this analysis.
18.5 Quality Control
Log the quality control (QC) data on forms QC-34 through QC-39 (Appendix B, figures B-86
through B-89); refer to Section 3.0 for additional information concerning these internal quality
control checks.
Calibration 5/a/7Ars~Calibration blanks (0.00 mg S/L standard) should be analyzed before the
initial sample analysis, at specified intervals thereafter (e.g., after every ten samples) and after
the last sample of each batch. Measured results for each blank should be 0.025 mg S/L or less.
If any blank is higher than this limit, check the system and reanalyze all samples since the last
acceptable calibration blank.
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Reagent B/anks-Tnree reagent blanks are analyzed with each batch of samples. These
blanks consist of the adsorption solutions (0 - 01 water, 2, 4, 8, 16, and 32 mg S/L) passed
through the analytical procedure without any soil being present. The reagent blanks should fall
between: 1.94 to 2.06 for SO4 2, 3.88 to 4.12 for S04 4, 7.76 to 8.24 for SO4 8, 15.52 to 16.48 for
SO4 16, and 31.36 to 32.64 for SO4 32. The reagent blank should be 0.025 mg S/L or less for SO4
0.
ffep/fcates-Orts sample from each batch should be weighed, extracted, and analyzed in
duplicate for extracted sulfate calculated as mg S/L The percent relative standard deviation
(%RSD) should meet the limits listed in Table 3-3.
QC Standarcfs-Tbese standards should be prepared from standards having the same
composition as the stock standard but from a separate source of sulfate. One detection limit
quality control check standard (DL-QCCS) having a known concentration of about 0.3 mg S/L
should be analyzed with each batch of samples. Measured values should be within 20 percent of
the known value.
QCCSs of concentrations at about mid-calibration range of the samples being analyzed
should be measured before the first sample, at specified intervals thereafter (e.g., every tenth
sample) and after the last sample of each batch of samples for both extracts. Measured values
for each QCCS should be within 5 percent of the known concentration.
Spike So/utton-For each batch of samples, a spike solution should be analyzed in triplicate
for S content. The spike solution consists of the adsorption solutions (0 - DI water, 2, 4, 8, 16,
and 32 mg S/L) associated with the appropriate analytical test being performed. Measured values
for the spike solution should be: t the contract required detection limit (CRDL); 0.025 mg S/L for
SO4.0; i 3 percent of the known value for SO4_2, S04_4, SO4_8, and SO4J6; and ± 2 percent of
the known value for S04_32.
Matrix Sp/'kes-For each batch of soils, the 2-, 8-, and 32-mg S/L isotherms from two
samples are spiked with known concentrations of sulfate. The concentration of sample plus
spike should be between 1.5 and 3 times the measured concentration of the sample with no
spike. In determining the recovery of the spike, the volume of the spike is assumed to be
negligible. Recovery should be 95 to 105 percent of the spike concentration.
QC Audit Sample (QCASJ-The QCAS should fall within the accuracy windows provided by
the quality assurance (QA) manager.
1C Resolution 7
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detection limits (IDLs) have been obtained, as outlined in Section 3.0 and Appendix A. Data
should be logged following the procedures described in Section 3.0.
NOTE: Figures within the square brackets, [ ], represent the form number and column in
which the data are entered.
18.6.1 Sample Preparation
1. Weigh 10.00 g air-dry sample to the nearest 0.01 g and place in a 100-mL centrifuge
tube. Log exact weight [34-B].
NOTE: If a 50-mL centrifuge tube is used, reduce sample weight to 5.00 g air-dry
mineral soil.
2. Add 50.0 ml of DI water to centrifuge tube and cap the tube. Mix contents with vortex
mixer until no soil adheres to the bottom of the centrifuge tube. If a 50-mL centrifuge
tube is used, reduce volume to 25.0 mL. Log [34-C].
3. Repeat steps 1 and 2 and substitute 2-, 4-, 8-, 16-, and 32-mg S/L solutions for DI
water. Log weight and volume data for 2 mg S/L, [35-B] and [35-C]; 4 mg S/L, [36-B]
and [36-C]; 8 mg S/L, [37-B] and [37-C]; 16 mg S/L, [38-B] and [38-C]; 32 mg S/L, [39-B]
and [39-C].
4. Shake the samples for 1 hour on a reciprocating shaker at a rate sufficient to maintain
the soil in suspension.
5. Centrifuge each sample until supernatant is clear.
6. Filter supernatant through a pre-rinsed 0.45-pm membrane filter.
7. Analyze solutions for sulfate by ion chromatography as described below.
18.6.2 Determination of Sulfate by Ion Chromatography
This procedure is based on methods employing Dionex ion chromatographs. Other
equivalent systems may be used with modifications to the columns, chromatographic conditions,
and reagents. In these cases, follow the recommendations of the manufacturer. Analyze both
the water and phosphate extracts of the soil samples.
18.6.2.1 Operating Specifications-
The following operating specifications and procedures are recommended for the Dionex-
type system. Other systems require similar procedures.
• Recording system, 10 or 30 pS/cm full scale deflection; 100 juS/cm for some cases;
linearity should be checked regularly since this may vary and cause error.
• Injection loop, 0.05 or 0.10 mL; 50 pi may be preferable for some phosphate samples
to reduce pH problems.
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• Flow rate, 2.0 to 2.3 mL/min.
• Pressure gauge or similar device, used as pump-stroke noise suppressor, as required
for unit.
NOTE: Make certain that pressure does not exceed the recommendations of the
manufacturer for the column.
18.6.2.2 Procedure-
1. Operate the fiber or micromembrane suppressor as recommended by the manufacturer.
Generally, the suppressor must be in an upright position with regenerant flowing from
bottom to top.
2. Set up the recorders or integrators for the most sensitive setting for the sample range
being analyzed. Set the second channel for a high range, or perform dilutions when
necessary. Operate integrators according to the instructions of the manufacturer.
3. Pump eluent through the columns. After a stable baseline is obtained, adjust the
recorder zero to approximately 10 percent of the chart. Inject the highest standard. As
the highest standard elutes, adjust the recorder range to approximately 90 percent of
the chart. Repeat several analyses of the highest standard to be certain that the gain
is stable and the peaks are reproducible. Analyze the resolution standard and determine
the resolution. If the phosphate-sulfate resolution does not exceed 60 percent, replace
or clean the separator column and repeat from Step 1.
4. Analyze the standards in random order. Load the injection loop, manually or via the
autosampler, with the standard to be analyzed. Load five to ten times the volume
required to flush the sample loop thoroughly; then inject the standard. Wash injector
loop thoroughly between each sample. For each analysis, measure and record the
peak height either manually or with a data system. If an integrator is available, record
the peak area.
5. Repeat Step 4 for analysis of QC samples, matrix spikes, blanks, and soil extracts. If
using an autosampler, fill it with the samples.
6. If any concentrations are above the range of the instrument, take an aliquot, dilute,
reanalyze, and report as follows:
Isotherm Aliquot Vol. Diluted Vol. Measured Cone.
0
2
4
8
16
32
[34-D]
[35-D]
[36-D]
[37-D]
[38-D]
[39-D]
[34-E]
[35-E]
[36-E]
[37-E]
[38-E]
[39-E]
[34-F]
[35-F]
[36-F]
[37-F]
[38-F]
[39-F]
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18.7 Calculations
NOTE: Designations within the square brackets, [ ], represent the form number and column
in which the data are entered on forms 34, 35, 36, 37, 38 and 39 (Appendix B, figures
B-80, B-81, B-82, B-83, B-84, and B-85.
Concentration (mg S/L) = Instrument Reading x Diluted Volume + Aliquot Volume
S04_0 [34-G] = [34-F] X ([34-E] -s- [34-D])
S04_2 [35-G] = [35-F] x ([35-E] -i- [35-D])
SO4_4 [36-G] = [36-F] X ([36-E] -i- [36-D])
SO4_8 [37-G] = [37-F] X ([37-E] -i- [37-D])
SO4_16 [38-G] = [38-F] x ([38-E] -i- [38-D])
SO4_32 [39-G] = [39-F] X ([39-E] -s- [39-D])
18.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specification for Reagent Water, D-1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
Fernandez, I. 1983. Field Study Program Elements to Assess the Sensitivity of Soils to Acidic
Deposition Induced Alterations in Forest Productivity. Technical Bulletin No. 404. National
Council of the Paper Industry for Air and Stream Improvement, Inc., New York, New York.
Johnson, D. W., and D. E. Todd. 1983. Some Relationships Among Iron, Aluminum, Carbon, and
Sulfate in a Variety of Forest Soils. Soil Sci. Soc. Amer. J. 47:702-800.
Tabatabai, M. A. 1982. Sulfur, pp. 501-538 In: Methods of Soil Analysis: Part 2, Chemical and
Microbiological Properties. Agronomy Monograph No. 9, 2nd Edition. A. L Page, R. H. Miller,
and D. R. Keeney (eds.), American Society of Agronomy/Soil Science Society of America,
Madison, Wisconsin.
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19.0 Total Carbon and Nitrogen
19.1 Overview
Carbon and nitrogen are major components of soil organic material; quantification of them
provides information about the amount and nature of organic material in the soil. Characterization
of organic C and N also provides insight about the potential for uptake or release of nitrogen and/or
sulfur by the soil organic matter due to microbial activity. Organic content of a soil affects sulfate
adsorption and cation exchange properties of the soil, and organic content is used for certain soil
taxonomic classifications. Carbon and nitrogen can occur in soils as inorganic forms (carbonates,
nitrate, and ammonium); methods for analyses of inorganic forms are not included here. Inorganic
forms of C and N are assumed to represent a minor fraction of total C and N in soils potentially
sensitive to acid deposition. Analyses of total carbon and nitrogen were conducted using
automated elemental analyzers.
19.1.1 Summary of Method
After sample processing and analysis for moisture content (sections 4.0 and 8.0), a soil
sample is oxidized at temperatures greater than 1,000 *C with catalysts as specified by the
instrument manufacturer. The evolved gases (CO2 and N2) are determined by thermal conductivity
or infrared (IR) spectroscopy.
19.1.2 Interferences
Although moisture can interfere with certain carbon-hydrogen-nitrogen (CHN) analyses by
producing large responses for total H, this interference can be eliminated in elemental analyses with
moisture traps. Drying can cause losses of volatile organic materials containing C and N, and
decomposition and loss of certain carbonates and ammonium salts. The samples may be freeze-
dried to minimize these losses if approved by the quality assurance (QA) manager. These analyses
are made on air-dry soils and the results corrected to an oven-dry basis.
Ambient N2 and C02 not associated with the sample present possible gaseous interferences.
Care must be taken with the blank to hold N2 and CO2 below the contract required detection limit
(CRDL). The use of high purity carrier gas or helium helps reduce CO2.
Soil residue can accumulate at the top of the combustion column. The column should be
cleaned if sufficient residue accumulates that analytical results are affected.
19.1.3 Safety
Wear protective clothing (laboratory coat and gloves) and safety glasses when preparing
reagents, especially when concentrated acids and bases are used. The use of concentrated acids
and hydroxide solutions should be restricted to a fume hood. Heat resistant gloves may be needed
when placing samples in the furnace. The furnace must be adequately vented and protected from
human contact and combustible materials. Gas cylinders should be bolted or chained in an upright
position.
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19.2 Sample Collection, Preservation, and Storage
A subsample is taken from the bulk soil sample after it has been air dried, homogenized, and
tested for moisture content (see sections 4.0 and 8.0). Samples should be stored at 4 *C until ready
for analysis.
NOTE: The subsample may be ground to pass a No. 60 (U.S. No.) or No. 100 seive, if desired.
19.3 Equipment and Supplies
19.3.1 Apparatus and Equipment
NOTE: This list is generic for C and N methods. The specific requirements will vary with the
instrument and procedures used. Some additional apparatus may be required; other
equipment may not be needed.
1. Analyzer for Total C and N, Carlo-Erba model 1500 or equivalent.
2. Balance, capable of weighing to ±0.001 mg (±1 /jg).
3. Balance calibration weights, 3-5 weights covering expected range.
19.3.2 Reagents and Consumable Materials
1. Catalysts and combustion accelerators (as needed).
2. Oxygen with in-line filter (high purity).
3. Carrier gases with in-line filter (as needed).
4. Standard Reference Material (SRM) 1646 (National Bureau of Standards [NBS]-standard
estuarine sediment; 1.84% C, 0.176% N). NBS lists, but does not certify, a 0.96 percent
sulfur content for this sample (Seward, 1988). Three years of Total C and N data for this
standard are documented by G. Cutter, Old Dominion University, Norfolk, Virginia ( personal
communication, August 1988).
5. Absorbents (as needed).
6. Water-Water used in all preparations should conform to ASTM specifications for Type I
reagent grade water (ASTM, 1984).
7. Vials, crucibles, boats, or tin sample capsules.
8. Forms-Form 40 total carbon, Form 41 total nitrogen, Form QC-40, and Form QC-41
(Appendix B, figures B-92 through B-95, respectively).
19.4 Calibration and Standardization
Follow the instrument manufacturer's instructions regarding calibration and standardization.
In general, the instrument should be calibrated at least once per day or once per batch of samples,
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whichever is more frequent. Use either NBS reference materials or standards supplied by the
manufacturer and approved by the laboratory or QA manager. The concentration range of the
standards must be representative of the C and N concentrations in the soil samples. Use a sample
of SRM 1646 as an initial calibration check.
If the nitrogen peak tends to consistently increase it may indicate that oxygen gas is
overshadowing the nitrogen peak. If this is the case, replace or regenerate the copper oxide
scrubber.
Combustion accelerators may be necessary if incomplete combustion occurs. Use vanadium
pentoxide or consult manufacturer's recommendations.
19.5 Quality Control
Log all QC data on Form QC-40 or QC-41 (Appendix B, figures B-94 and B-95, respectively);
refer to Section 3.0 for additional details concerning the internal QC checks.
Calibration £/a/?/rs--Calibration blanks should be analyzed before the initial sample analysis,
at specified intervals thereafter (e.g., after every ten samples) and after the last sample of each
batch for both carbon and nitrogen. If the instrument does not produce a blank value in weight
percentage, the value should be determined from the instrument readout (or blank used in calibration
and standardization), the instrumental factor (relating read-out to weight, pg, of element), and an
appropriately assumed sample size (the smallest acceptable weight given by the manufacturer of
the instrument; in general, 0.1 mg). Each blank should be less than the CRDL listed in Table 3-2.
If any blank is higher than this limit, check the system and reanalyze all samples since the last
acceptable calibration blank.
Reagent Blanks-Three reagent blanks are analyzed with each batch of samples if catalysts
or accelerators are used. Each blank should be less than the CRDL outlined in Table 3-2. No
reagent blanks are necessary if catalysts or accelerators are not used.
Rep/icates-One sample from each batch should be analyzed in duplicate for total carbon and
nitrogen. The percent relative standard deviation (%RSD) of the paired data should be 10 percent
or less.
QC Standards-One detection limit quality control check standard (DL-QCCS) having a known
concentration of about 0.03 weight percent for Total C and 0.015 weight percent for Total N should
be analyzed with each batch of samples. Measured values should be within 20 percent of the
known value.
Quality Control Check Standards (QCCSs) of concentrations at about mid-calibration range
of the samples being analyzed should be measured before the first sample, at specified intervals
thereafter (e.g., every tenth sample) and after the last sample of each batch of samples. Measured
values of each QCCS should be within 10 percent of the known concentrations.
Matrix Spikes-Pot each batch of soils one sample is spiked with a standard containing known
concentrations of carbon and nitrogen. The spike is weighed into the combustion capsule or boat
before the sample is added. The concentration of sample plus spike should be between 1.5 and 3
times the measured concentration for each element in the sample with no spike. The amount of
added spike is determined by multiplying the known concentration of the spike by the spike weight,
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divided by the weight of the sample being spiked. In determining the concentration of the sample
plus spike, the weight of the spike is assumed to be negligible. Recovery should be 90 to 110
percent of the spike concentration.
QC Audit Sample (QCAS)~~ft\e QCAS should fall within the accuracy windows provided by the
QA manager.
19.6 Analytical Procedures
Before proceeding with the analytical procedure, the analyst should be certain that all QC
procedures have been implemented, all labware has been properly cleaned, and valid instrumental
detection limits (IDLs) have been obtained, as outlined in Section 3.0 and Appendix A. Data should
be logged following the procedures described in Section 3.0.
NOTE: Figures within the square brackets, [ ], represent the form number and column in
which the data are entered.
1. Follow manufacturer's instructions to determine instrument factors and log in Total C, [40-
CJ; Total N, [41-C].
2. Weigh approximately 100 mg of air-dry mineral soil or 20 mg of organic soil and log exact
weight for Total C [40-B]; and Total N, [41-BJ.
3. Perform analyses and blanks as recommended by instrument manufacturer and log the
instrumental read-out for Total C, [40-D], [40-E]; and Total N, [41-D], [41-E]; in appropriate
units.
Note: Raw data on forms 40 and 41 (Appendix B, figures B-92 and B-93) are on an air-
dry basis.
19.7 Calculations
NOTE: Designations within the square brackets, [ ], represent the form number and column
in which the data are entered on forms 40, 41, and 1 (Appendix B, figures B-92, B-93,
and B-9.
Element (Wt %) = {([instrument reading] - [blank]) x [instrument factor] x 1} +
{[sample wt.] x (1 - [MOISTURE]) + (100 + [MOISTURE]) x 100
C_TOT [40-F] = {([40-D] - [40-E]) x [40-C] x 1} + {[40-B] x (1 - [1-D]) + (100 + [1-D])} x 100
NJOT [41-F] = {([41-D] - [41-E]) x [41-C] X 1} + {[41-B] X (1 - [1-D]) + (100 + [1-D])} X 100
19.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specification for Reagent Water, D-1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
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Seward, R. W. (ed). 1988. National Bureau of Standards Standard Reference Materials Catalog
1988-89. NBS Special Publication 260, U.S. Government Printing Office, Washington, D.C.
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20.0 Total Sulfur
20.1 Overview
The determination of total sulfur is useful for characterizing relationships between inputs of
sulfur from acidic deposition and soil sulfur pools. In this method, total sulfur in soil samples is
determined with an automated sulfur analyzer by combustion of the sample at approximately
1,370 *C. This procedure is based on the operating instructions for a LECO SC-132 sulfur analyzer
(LECO Corporation, 1983), adapted to permit analysis of very low levels of total S (as low as 10
mg/L) in soils.
20.1.1 Summary of Method
The sample is placed in a ceramic crucible with combustion accelerators and heated to a
maximum of 1,370 *C in a resistance furnace. The combustion of the sample liberates SO2 which
is determined by an infrared (IR) detector. A microprocessor calculates results by combining the
outputs of the infrared detector and system ambient sensors with preprogrammed calibration,
linearization, and mass compensation factors. This method is based on research by David et al.
(1989).
20.1.2 Interferences
If the soil has a high organic matter content, sample size must be reduced to prevent an
explosion in the furnace when heat and oxygen are added. Also, high organic matter content may
delay combustion. Low recovery of sulfur may occur, since organic matter consumes oxygen to
produce CO2 and nitrogen oxides in addition to SO2.
20.1.3 Safety
Wear protective clothing (laboratory coat and gloves) and safety glasses when preparing
reagents, especially when concentrated acids and bases are used. The use of concentrated acids
and hydroxide solutions should be restricted to a fume hood. Heat resistant gloves may be needed
when placing samples in the furnace. The furnace must be adequately vented and protected from
human contact and combustible materials. Gas cylinders should be bolted or chained in an upright
position.
Fumes of magnesium oxide (MgO) are toxic. Magnesium perchlorate [MgJCIOJJ is a fire and
explosion hazard if it comes in contact with organic materials.
20.2 Sample Collection, Preservation, and Storage
A subsample is taken from the bulk soil sample after it has been air dried, homogenized, and
tested for moisture content (see sections 4.0 and 8.0). Samples should be stored at 4 *C until ready
for analysis.
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NOTE: The subsample may be ground to pass a No. 60 (U.S. No.) or No. 100 sieve, if desired.
20.3 Equipment and Supplies
20.3.1 Apparatus and Equipment
1. Sulfur analyzer, LECO model SC-132, or equivalent.
2. Sampling scoops (LECO or equivalent).
3. Balance, capable of weighing to ±0.01 mg.
4. Balance calibration weights, 3-5 weights covering expected range.
20.3.2 Reagents and Consumable Materials
1. Oxygen (high purity).
2. Anhydrous magnesium perchlorate [MgfCIOJJ, 10-20 mesh, or equivalent desiccant
specified by manufacturer for drying gases (after combustion and prior to detection).
3. Carrier gases (if needed).
4. Water-Water used in all preparations should conform to ASTM specifications for Type
I reagent grade water (ASTM, 1984).
5. Combustion boats, sulfur-free and appropriate for use with the equipment used.
6. Forms-Form 42, Total sulfur and Form QC-42 (Appendix B, figures B-96 and B-97,
respectively).
NOTE: Certain instruments may not require the following materials. Refer to the
instruction manual for the specific instrument and consult with the quality
assurance (QA) manager.
7. Magnesium oxide (MgO), powder, American Chemical Society (ACS) reagent grade, low
in sulfur.
8. V2O5. LECO Part No. 501-636.
9. LECO orchard leaves (0.169% S) for calibration.
10. National Bureau of Standards (NBS) Standard Reference Material (SRM) 1633a Coal Fly
Ash (0.18% S).
20.4 Calibration and Standardization
Follow the procedure outlined in the operating manual of the specific instrument. Generally,
the following steps are necessary:
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1. Run up to five analyses to condition the instrument at the beginning of the day, whenever
the instrument has been idle for a period of time, or whenever new desiccant has been
installed.
2. Periodically, check the desiccant (magnesium perchlorate) in the drying tube and replace
it whenever the first few centimeters become wet. If it becomes too wet, the baseline
may shift as the sample starts to heat and this shift will be integrated with and
computed as sulfur.
3. To prolong the life of the combustion tube and refractory liner, the furnace should remain
at operating temperature at all times; however, to conserve energy the furnace
temperature may be reduced slightly. Refer to the instrument manual for specific
information.
The instrument should be calibrated once per day or once per batch, whichever is more
frequent. Analyze a series of LECO orchard leaves (0.169% S) by the procedure given in the
instruction manual for the specific instrument. Determine the weights of standard to use so that
the analytical results for the standard bracket the expected sulfur content of the samples. Check
calibration by running NBS sample SRM 1633a (0.18% S) before routine analysis.
Analyze no fewer than three standards that bracket the expected concentration range of the
samples. When only one standard material is used for calibration, at least three samples of
standard material of different weights are prepared such that: (1) the amount of sulfur produced
by the smallest sample is approximately three to five times the instrument detection limit, (2) the
amount of sulfur produced by the largest sample is above that of the actual samples, and (3) the
amount of sulfur produced by the intermediate sample is in the mid-range of the analyte content of
the samples. The values for these check samples should be within the contract specified limits.
20.5 Quality Control
Log all QC data on Form QC-42 (Appendix B, Figure B-97); refer to Section 3.0 for additional
details concerning the internal QC checks.
Calibration £?/a/7/rs~Calibration blanks should be analyzed before the initial sample analysis,
at specified intervals thereafter (e.g., after every ten samples) and after the last sample of each
batch. If the instrument does not produce a blank value in weight percentage, the value should be
determined from the instrument readout (or blank used in calibration and standardization), the
instrumental factor (relating read-out to weight, ^g, of element), and an appropriately assumed
sample size (the smallest acceptable weight given by the manufacturer of the instrument; in general
0.1 mg). Each blank should be less than the contract-required detection limit (CRDL) listed in Table
3-2. If any blank is higher than this limit, check the system and reanalyze all samples since the last
acceptable calibration blank.
Reagent B/anks-Tbree reagent blanks, consisting of 1.0 g of V2O5, are analyzed with each
batch of samples. Each blank should be less than the CRDL outlined in Table 3-2.
Replicates-One sample from each batch should be analyzed in duplicate. The percent relative
standard deviation (%RSD) of the paired data should be 10 percent or less.
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QC Standards-One detection limit quality control check standard (DL-QCCS) having a known
concentration of about 0.003 percent S should be analyzed with each batch of samples. Measured
values should be within 20 percent of the known value.
QCCSs of concentrations at about mid-calibration range of the samples being analyzed should
be measured before the first sample, at specified intervals thereafter (e.g., every tenth sample) and
after the last sample of each batch of samples. Measured values of each QCCS should be within
10 percent of the known concentrations.
Matrix Sp/kes-For each batch of soils, one sample is spiked with a standard containing a
known concentration of sulfur. The spike is weighed into the combustion capsule or boat before
the sample is added. The concentration of sample plus spike should be between 1.5 and 3 times
the measured concentration for each element in the sample with no spike. The amount of added
spike is determined by multiplying the known concentration of the spike by the spike weight, divided
by the weight of the sample being spiked. In determining the concentration of the sample plus
spike, the weight of the spike is assumed to be negligible. Recovery should be 90 to 110 percent
of the spike concentration.
QC Audit Sample (QCASJ-The QCAS should fall within the accuracy windows provided by the
QA manager.
20.6 Analytical Procedure
Before proceeding with the analytical procedure, the analyst should be certain that all QC
procedures have been implemented, all labware has been properly cleaned, and valid instrumental
detection limits (IDLs) have been obtained, as outlined in Section 3.0 and Appendix A. Data should
be logged following the procedures described in Section 3.0.
NOTE 1: Figures within the square brackets, [ ], represent the form number and column in
which the data are entered.
NOTE 2: This method is based on David et al. (1989).
1. Weigh approximately 0.800 g of mineral soil (or 0.300 g of organic soil) into a new ceramic
combustion boat using the integral balance (nearest 1 mg) and log exact weight in [42-B].
2. Add 1.00 g of V205 iron powder (LEGO Part No. 501-636) to the boat. Mix the sample
thoroughly with accelerators, taking care not to lose any sample material. Reproducible
results for low concentration samples are dependent on thorough mixing.
3. Follow step-by-step analytical procedure as outlined in the instrument instruction manual.
20.7 Calculations
NOTE: Designations within the square brackets, [ ], represent the form number and column
in which the data are entered on forms 42 and 1 (Appendix B, figures B-96 and B-9).
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An instrument with internal calibration may report sulfur results in weight percent, although
correction for moisture content of soil is still required.
Sulfur (Wt %) = {[Instrument reading] x 1} + {[sample wt.J x (1 - [MOIST]) +
(100 -I- [MOIST]) x 100}
SJOT [42-F] = {[42-D] x 1} + {[42-B] x (1 - [1-D]) + (100 + [1-D]) x 100}
Data from other instruments may require a series of calculations to express results as weight
percent sulfur. Compare the sample results to a standard curve. Determine the sulfur content in
mg, then convert to weight percent, as follows:
% Sulfur = mg S/g x 1000 mg/g x 100
SJOT [42-F] = {[42-D] X 0.1 x 1} + {[42-B] X (1 - [1-D]) + (100 + [1-D])} X 100
20.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specification for Reagent Water, D-1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
David, M. B., M. J. Mitchell, D. Aldcorn, and R. B. Harrison. 1989. Analysis of Sulfur in Soil, Plant and
Sediment Materials: Sample Handling and use of an Automate Analyzer. Soil Biology and
Biochemistry. 21:119-123.
LECO Corporation. 1983. Instruction Manual S0132. LECO Corporation, 300 Lakeview Ave., St.
Joseph, Michigan 49085.
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Appendix A
General Laboratory Procedures
Logbooks should be kept for each procedure or instrument. The logbook entries should
include, at a minimum, all raw data, instrument and analyst identification, date and time of analysis,
and comments on any unusual occurences or protocol deviations. The laboratory supervisor should
review and sign the logbook at the completion of daily analyses. There should also be an
instrument calibration logbook, including a record of the dates on which new chemicals are opened.
Correct errors by writing a single line through the error and initialing the error. Always use ink when
recording in the logbook.
NOTE: Gloves, lab coats, and safety glasses should be worn when contacting a sample,
acids, or hazardous materials.
A.1 Cleaning Procedures for Labware
Clean all labware that comes into contact with the samples (e.g., sample bottles, centrifuge
tubes, autosampler tubes, and cups) as described below.
A. 1.1 Initial Cleaning
For new plastic ware, rinse each container with reagent grade methanol or ethanol. When
cleaning plastic ware for reuse, the alcohol rinse may be omitted. Repeat this step if an oily residue
appears during any analysis. Glassware does not need to be precleaned with alcohol.
A. 1.2 Cleaning Reusable Labware
After an initial wash with tapwater, rinse each container three times with deionized (DI) water,
three times with 3 N HCI (1:3 concentrated HCI:DI water), and three times with DI water as a final
rinse.
After the initial cleaning, check 5 percent of the containers to ensure that rinsing has been
adequate. Perform the check as follows:
Add 500 mL of DI water to each clean, dry container or add the maximum volume if the
capacity of the container holds less than 500 mL Seal the container with a cap or with
Parafilm, then rotate the container slowly until the water touches all surfaces. Allow the
container to sit overnight. Remove the cap and measure the conductivity of the contained
water. The conductivity must be less than 1 /vS/cm. If any of the containers fail the check.
rerinse all the containers and perform the check again on 5 percent of the rerinsed containers.
After the final rinse, empty the container, invert it, and allow it to dry. All plastic ware should
be air-dried; glassware may be air-dried or oven-dried.
Place the plastic containers, capped or covered with Parafilm, in plastic bags which will remain
sealed until the containers are used for sample analysis. Store glassware in a dust-free
environment.
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Syringes and centrifuge tubes may require the use of a brush and neutral pH detergent to
remove adhering soil particles. A detergent wash must be followed by at least three tap-water
rinses followed by three DI water rinses. Containers should be checked as described above.
Kjeldahl flasks should be cleaned with sulfuric acid because it is a good scavenger for
ammonium ion.
Sedimentation cylinders may be cleaned by three deionized water rinses. The acid rinse may
be omitted. Brushing may be required to remove adhering soil particles and, in extreme cases, a
detergent wash followed by at least three tap-water rinses and three deionized-water rinses may
be used.
A.2 Electronic Balance
A.2.1 Balance Standardization
Check standardization weekly and both prior to and after weighing chemicals used in preparing
primary standards. Be sure to check the calibration over the entire range for which the balance is
used.
1. While wearing gloves, use calibration weights ("S" class weights for analytical balances
or "P" class weights for top-loading balances) to standardize the balance. Do not touch
the weights with anything but forceps. Tare the balance and record the reading for each
weight in the instrument calibration logbook.
2. If weight values and balance readings do not agree, consult the manufacturer's guide
for adjustments.
A.2.2 Weighing Procedures
Always use a dry Teflon spatula. Do not use same spatula for successive weighings of
different chemicals. Remember to weigh the substance with the lid on the balance if the balance
had been originally tared with the lid on.
1. While wearing gloves, pour the approximate amount of substance needed into a
weighboat. Do not put the spatula into the bottle.
2. Obtain a second weighboat, place it on the balance and tare.
3. Using a spatula, transfer the substance to the weighboat on the balance until the
desired amount is obtained.
4. Dispose of any unused substance; do not return to bottle.
A.2.3 Cleanup
1. Rinse the spatula with deionized water after use and allow it to air dry.
2. Do not leave any spilled chemicals on the balance. Use a damp Kimwipe to clean the
balance pan and wipe it dry.
-------
Appendix A
Revision 0
Date: 8/90
Page 3 of 4
A.3 Micropipet
The following instructions refer to the Finn continuous volume micropipets. These procedures
can be modified for use with other digital micropipets. Keep pipet vertical at all times to prevent
contamination.
A.3.1 Pipet Calibration
NOTE: Check the calibration of each pipet weekly, at a minimum, and record data in the
instrument calibration logbook. Each procedure requires a daily calibration check of
all pipets used. These data are recorded in the corresponding procedural logbook.
1. Calibrate pipets as follows, setting the volume as instructed below:
Pipet Volume Range Set Volume to: Permitted Ranges
40-200 \i\- 50 juL 0.049-0.051 g
200-1000 pi 1000 pi 0.990-1.010 g
1000-5000 pL 2000 /^L 1.990-2.010 g
2. While wearing gloves, place the appropriate size pipet tip onto the end of the pipet.
3. Using the balance, set for low range (0-30 g), place a weighboat on the balance and
tare. Use fresh deionized water and pipet the specified volume into weighboat. Weigh
01 water a total of five separate times and average to nearest 0.1 mg and compare this
average with the permissible ranges in Step 1. Record all measurements in the
instrument calibration logbook.
4. If the mean in Step 3 lies outside of the permitted range, the volume setting should be
adjusted according to manufacturer's instructions.
A.3.2 Pipet Operation - Forward Technique
NOTE: Operate the thumb button slowly and steadily. Do not let the thumb button snap
back. Deliver the volume smoothly.
1. While wearing gloves, place a clean pipet tip on pipet.
2. Keep the pipet as vertical as possible during uptake of solution. Depress thumb button to
first stop. Dip the pipet tip slightly below the solution surface and slowly release the
thumb button.
3. Deliver the liquid by gently depressing the thumb button to the first stop. Touch the pipet
tip to side of the container (except when preserving aliquots) while simultaneously
depressing the thumb button to the second stop. Slowly release the thumb button.
4. Remove the used pipet tip by pressing the tip ejector down. Dispose of the pipet tip in a
proper waste receptacle.
-------
Appendix A
Revision 0
Date: 8/90
Page 4 of 4
A.3.3 Pipet Operation - Reverse Technique
NOTE: Use this technique to pipet viscous liquids.
1. Apply a pipet tip and depress thumb button to second stop. Dip the pipet tip slightly below
the surface of the solution and slowly release the thumb button.
2. Deliver the liquid by gently depressing the button to the first stop. Release the thumb
button. Remove and dispose of the pipet tip.
A.3.4 Care of Pipets
1. If any liquid is sucked into the barrel, immediately consult the manufacturer's guide and
clean as directed. Do not use pipet until it is cleaned.
2. For leakage or inaccuracies refer to the manufacturer's troubleshooting guide.
A.4 Repipet Dispenser Instructions
These instructions are specific to the Reference Lab Industries' Repipet used in the AERP
studies. These procedures may be modified for use for other equivalent apparatus. Do not include
the drops that are dispensed when pulling up on the Repipet dispenser in the delivery volume.
A.4.1 Calibration of 2.0-mL, 5.0-mL, or 10-mL Repipet Dispensers
1. Set the Repipet to dispense 2.0, 5.0, or 10 ml of solution as directed by manufacturer.
2. Place the weighboat on the balance and tare. Fill the Repipet bottle with DI water and
dispense 2.0, 5.0, or 10 mL of DI water into the weighboat.
3. Return the weighboat to the balance and weigh contents. Acceptable limits are:
Repipet Limits
2.0 mL 2.0 ± 0.02 g
5.0 mL 5.0 t 0.05 g
10.0 mL 10.0 ± 0.10 g
If weight is outside range, adjust dispenser as directed by manufacturer and recheck.
-------
Appendix B
Revision 0
Date: 8/90
Page 1 of 103
Appendix B
Direct/Delayed Response Project Blank Data Forms
The Direct/Delayed Response Project forms shown in this appendix are facsimiles of the forms
used in the preparation and analytical laboratories.
Figure Number Form Title Page
B-1 Field data form. 4 of 103
B-2 Sample receipt raw data form. 8 of 103
B-3 Bulk sample processing raw data form. 9 of 103
B-4 Clod bulk density raw data form. 10 of 103
B-5 Known volume bulk density raw data form. 11 of 103
B-6 Field-moist pH raw data form. 12 of 103
B-7 Loss-on-ignition raw data form. 13 of 103
B-8 Air-dry moisture raw data form. 14 of 103
B-9 Form 1, air-dry moisture parameter data. 15 of 103
B-10 Form QC-1, quality control data for air-dry moisture
content. 16 of 103
B-11 Form 2, particle size parameters (raw data). 17 of 103
B-12 Form 3, particle size parameters (calculated data). 18 of 103
B-13 Form QC-2, quality control particle size parameters
(raw data). 19 of 103
B-14 Form QC-3, quality control particle size parameters
(calculated data). 20 of 103
B-15 Form 4, pH in water. 21 of 103
B-16 Form 5, pH in 0.01 M calcium chloride. 22 of 103
B-17 Form QC-4, quality control parameter pH in water. 23 of 103
B-18 Form QC-5, quality control parameter pH in 0.01 M
calcium chloride. 24 of 103
B-19 Form 6A, cation exchange capacity-ammonium acetate
(flow injection analysis). 25 of 103
B-20 Form 6B, cation exchange capacity-ammonium acetate
(titration method). 26 of 103
B-21 Form 7A, cation exchange capacity-ammonium chloride
(flow injection analysis). 27 of 103
B-22 Form 7B, cation exchange capacity-ammonium chloride
(titration method). 28 of 103
B-23 Form QC-6A, quality control parameter cation exchangeable
capacity-ammonium acetate (flow injection analysis). 29 of 103
B-24 Form QC-6B, quality control parameter cation exchangeable
capacity-ammonium acetate (titration method). 30 of 103
B-25 Form QC-7A, quality control parameter cation exchangeable
capacity-ammonium chloride (flow injection analysis). 31 of 103
-------
Appendix B
Revision 0
Date: 8/90
Page 2 of 103
B-26 Form QC-7B, quality control parameter cation exchangeable
capacity-ammonium chloride (titration method). 32 of 103
B-27 Form 8, calcium in ammonium acetate. 33 of 103
B-28 Form 9, magnesium in ammonium acetate. 34 of 103
B-29 Form 10, potassium in ammonium acetate. 35 of 103
B-30 Form 11, sodium in ammonium acetate. 36 of 103
B-31 Form QC-8, quality control calcium in ammonium acetate. 37 of 103
B-32 Form QC-9, quality control magnesium in ammonium acetate. 38 of 103
B-33 Form QC-10, quality control potassium in ammonium acetate. 39 of 103
B-34 Form QC-11, quality control sodium in ammonium acetate. 40 of 103
B-35 Form 12, calcium in ammonium chloride. 41 of 103
B-36 Form 13, magnesium in ammonium chloride. 42 of 103
B-37 Form 14, potassium in ammonium chloride. 43 of 103
B-38 Form 15, sodium in ammonium chloride. 44 of 103
B-39 Form 16, aluminum in ammonium chloride. 45 of 103
B-40 Form QC-12, quality control calcium in ammonium chloride. 46 of 103
B-41 Form QC-13, quality control magnesium in ammonium chloride. 47 of 103
B-42 Form QC-14, quality control potassium in ammonium chloride. 48 of 103
B-43 Form QC-15, quality control sodium in ammonium chloride. 49 of 103
B-44 Form QC-16, quality control aluminum in ammonium chloride. 50 of 103
B-45 Form 18, pH in 0.002 M calcium chloride. 51 of 103
B-46 Form 19, calcium in 0.002 M calcium chloride. 52 of 103
B-47 Form 20, magnesium in 0.002 M calcium chloride. 53 of 103
B-48 Form 21, potassium in 0.002 M calcium chloride. 54 of 103
B-49 Form 22, sodium in 0.002 M calcium chloride. 55 of 103
B-50 Form 23, iron in 0.002 M calcium chloride. 56 of 103
B-51 Form 24, aluminum in 0.002 M calcium chloride. 57 of 103
B-52 Form QC-18, quality control pH in 0.002 M of calcium chloride. 58 of 103
B-53 Form QC-19, quality control calcium in 0.002 M calcium chloride. 59 of 103
B-54 Form QC-20, quality control magnesium in 0.002 M calcium chloride. 60 of 103
B-55 Form QC-21, quality control potassium in calcium chloride. 61 of 103
B-56 Form QC-22, quality control sodium in 0.002 M calcium chloride. 62 of 103
B-57 Form QC-23, quality control iron in 0.002 M calcium chloride. 63 of 103
B-58 Form QC-24, quality control aluminum in 0.002 M calcium chloride. 64 of 103
B-59 Form 17, barium chloride-TEA acidity. 65 of 103
B-60 Form QC-17, quality control barium chloride-TEA acidity. 66 of 103
B-61 Form 25, pyrophosphate extractable iron. 67 of 103
B-62 Form 26, prophosphate extractable aluminum. 68 of 103
B-63 Form 27, acid oxalate extractable iron. 69 of 103
B-64 Form 28, acid oxalate extractable aluminum. 70 of 103
B-65 Form 29, acid oxalate extractable silicon. 71 of 103
B-66 Form 30, citrate dithionite extractable iron. 72 of 103
B-67 Form 31, citrate dithionite extractable aluminum. 73 of 103
B-68 Form QC-25, quality control pyrophosphate extractable iron. 74 of 103
B-69 Form QC-26, quality control pyrophosphate extractable aluminum. 75 of 103
B-70 Form QC-27, quality control acid oxalate extractable iron. 76 of 103
B-71 Form QC-28, quality control acid oxalate extractable aluminum. 77 of 103
B-72 Form QC-29, quality control acid oxalate extractable silicon. 78 of 103
-------
Appendix B
Revision 0
Date: 8/90
Page 3 of 103
B-73 Form QC-30, quality control citrate dithionite
extractable iron. 79 of 103
B-74 Form QC-31, quality control citrate dithionite
extractable aluminum. 80 of 103
B-75 Form 32, water extractable sulfate. 81 of 103
B-76 Form 33, phosphate extractable sulfate. 82 of 103
B-77 Form QC-32, quality control water extractable sulfate. 83 of 103
B-78 Form QC-33, quality control phosphate extractable sulfate. 84 of 103
B-79 1C Form, quality control: ion chromotography
resolution test. 85 of 103
B-80 Form 34,0 mg S/L isotherm. 86 of 103
B-81 Form 35,2 mg S/L isotherm. 87 of 103
B-82 Form 36,4 mg S/L isotherm. 88 of 103
B-83 Form 37,8 mg S/L isotherm. 89 of 103
B-84 Form 38, 16 mg S/L isotherm. 90 of 103
B-85 Form 39, 32 mg S/L isotherm. 91 of 103
B-86 Form QC-34, quality control zero mg S/L isotherm parameter. 92 of 103
B-87 Form QC-35, quality control two mg S/L isotherm parameter. 93 of 103
B-88 Form QC-36, quality control four mg S/L isotherm parameter. 94 of 103
B-89 Form QC-37, quality control eight mg S/L isotherm parameter. 95 of 103
B-90 Form QC-38, quality control sixteen mg S/L isotherm parameter. 96 of 103
B-91 Form QC-39, quality control thirty-two mg S/L
isotherm parameter. 97 of 103
B-92 Form 40, total carbon. 98 of 103
B-93 Form 41, total nitrogen. 99 of 103
B-94 Form QC-40, quality control total carbon. 100 of 103
B-95 Form QC-41, quality control total nitrogen. 101 of 103
B-96 Form 42, total sulfur 102 of 103
B-97 Form QC-42, quality control total sulfur. 103 of 103
-------
Appendix B
Revision 0
Date: 8/90
Page 4 of 103
U S DEPARTMENT OF AGRICULTURE.
SOIL CONSERVATION SERVICE
SOIL DESCRIPTION
SCS SOI 232
3 «7
SOIL SERIES REPRESENTED
1 1 1 1 1 1 1 t 1 I I 1 1 I 1 1 1
DATE
MO DAY YR
,1,1,
SITE ID s
ST COUNTY UNIT u
, 1 , , 1 , I l"
MLRA
1 1 1
LATITUDE D
DEC MIN SEC '
,1,1,1
LONGITUDE D
DEG MIN SEC '
1,1,1,1
"a
1 1
SHP
U A
I ,
a H
M S
1 |
ASP
DEG
1 1
PEDON CLASSIFICATION
O SO GG SO PSC MIN RX TMP OTH
I , I , I i . , I , . I , I t I , I ,
PRECIP
1 1
WATERTABLE
DEPTH DAYS
1 1 1 1 1
D
I
1
S
T
1
H
c
I
0
R
1
ELEVATION
till
PARENT MATERIAL
1 ?
W B M ORIG W R M
"1 I 1 1
0), j
ORIG W 8
1
®l
1
M
4
ORK,
1
W B M
0,
IT
ORIG H
, 1'
TEMPERATURES "C
AVERAGE AIR AVERAGE SOIL
ANN SUM WINTER
1 1 1 t 1 1 1 1
ANN SUM WINTER
1 1 1 1 1 I 1 1
MM
ROE
I
WLATHEfl
STATION NO
1 1 1 1 t
CONTROL
SECTION
1 1 1 1 1
Ml
WA
«N
<)l
DIAGNOSTIC VEA1UHES
DEPTH .K,
I I , I
I I ! I
I . . I'
I I I I
, I
J UEGEIATION SPECIES
I I I I I I I I I I
8 I 9 I 10
I I I I I 1 I I I , I I I I I I
DESCRIBERS NAMES
LOCATION DESCRIPTION
WATERSHED
ID
1
1 1 1 1
CLASS
1
ST
TRAN
OIR
1
SECT
DIST
1 1
CREW
ID
1 1 1
WATERSHED NAME
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 I..1.I
Figure B-1. Field data form (1 of 4).
-------
Appendix B
Revision 0
Date: 8/90
Page 5 of 103
1
2
3
4
b
6
7
3
9
10
DEPTH
I |
I i
I |
I |
I |
I I
I I
i I
I I
I I
I |
I I
I i
I I
] |
I |
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I !
I i
I I
HORIZON
DESIGNATIO
O
1
S MASTER
C LETTER S
| |
i |
1 1
| |
1 I
1 1
1 1
1 1
1 1
1 1
1
1
I
I
1
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1
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1
FREE FORM NOTE
MOIST COLOR
I I
I I I
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1 I I
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I 1
I I
I I
I I
I I
I I
I I
1
2
3
4
5
6
7
8
9
10
SAMPLE
NUMBERS
BULK DENSITY
T
N V
0 P
HORIZON NOTES
Figure B-1. Field data form (2 of 4).
-------
Appendix B
Revision 0
Date: 8/90
Page 6 of 103
Figure B-1. Field data form (3 of 4).
-------
Appendix B
Revision 0
Date: 8/90
Page 7 of 103
EFFER-
V£S
CENCE
C A E
L 0 X
| |
I ]
1 1
I |
1 1
I |
| |
! 1
L I
I 1
FIELD
MEASURED
PROPERTIES
KND AMOUNT
P 1
C |L
|
P 1
C |L
|
P 1
C H
I
P 1
c |L
I
f I
C |L
1
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p 1
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1 1
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1 [
i i
i i
i 1
1 1
i ]
i 1
i i
i i
1 1
1 I
i i
FIELD
MEASURED
PROPERTIES
KND AMOUNT
1
1
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]
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ROCK
FRAGMENTS
K R
N N S
D % D Z
1
1
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ROCK
FRAGMENTS
K R
N N
D % D
1
1
1
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I
1
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FREE FORM NOTES
LOG
WEATHER
SET I.D
UNDERSTORY VEG.
SLIDES »S PED FACE
UNDERSTORY
OVERSTORY
LANDSCAPE
Figure B-1. Field data form (4 of 4).
-------
Appendix B
Revision 0
Date: 8/90
Page 8 of 103
SOU SAMPLE RECEIPT IORX
SAM CODE
CREW
ID
sm
IP
SET
ID
DATE
SAMPLED
DATE
SHIPPED
DATE
RECEIVED
RECEIVED
BT
SAKPLZ CONDITION
HET/DRI (H/D) BAG SPLIT (1/S)
SIEVED/TOSIEVED (S/D)
TODER VOLUXZ (W)
CLOD
S UMBER
mom
VOLUKE
CAVITI
SAXPLS
NOHBER
COXHEXTS
- -
Figure B-2. Sample receipt raw data form.
-------
SAMPLE ID:
SITE ID:
SET ID:
BATCH ID:
BULK SAMPLE RAW DATA
OATE SAMPLED:
DATE REC'D:
PROCESS START:
PROCESS COMPLETE:
SOIL TYPE: M/0
Initials:
FIELD pK:
Initials:
AIR SAMPLE DRYING:
Date % Moisture Initial?
Data:
TOTAL BULK WT:
Initials:
2 to 4.75 mm:
Date:
ROCK FRAGMENT WT:
_. g 4.75 to 20 mm:
Initials:
ENTERED IN COMPUTER: Date:
Initials:
COMMENTS:
Appendix B
Revision 0
Date: 8/90
Page 9 of 103
Figure B-3. Bulk sample processing raw data form.
-------
CLOD BULK DENSITY RAW DATA
ALL HEIGHTS RECORDED TO 0.01 GRAMS
p»je I
riJ> «T TEKP
RIP FLD_DJ Boi»t7dry LAB DP LAB WI CLOD BJO C
CRUC
»0. R PRAG
PROS
PLOAT I/M ID COlffiZNTS
Figure B-4. Clod bulk density raw data form.
-0 O 33 >
u) CD CD tj
*S?f*
O CO
o
-------
Appendix B
Revision 0
Date: 8/90
Page 11 of 103
KNOWN VOLUME BULK DENSITY DATA
FACE
ALL HEIGHTS RECORDED TO 0.0 GRAMS
SAM CODE
AIR NT
OD HI
R FRAG
VOL
(CC.)
DATE
ID
COHKENTS
Figure B-5. Known volume bulk density raw data form.
-------
Appendix B
Revision 0
Date: 8/90
Page 12 of 103
pH RAW DATA
DATE
SAMPLE CODE
Init OCCS
D
QCCS
D
SAMP.
*
pH
SAMPLE CODE
QCCS
D
QCCS
Final QCCS
SAKP.
f
pH
Figure B-6. Field-moist pH raw data form.
-------
Appendix B
Revision 0
Date: 8/90
Page 13 of 103
SAMPLE LOSS ON IGNITION DATA
ALL WEIGHTS REPORTED IN 0.01 GRAMS
SAM CODE
CRUC.
NO.
AIR
NT.
0. 0.
NT.
ASHED
NT.
DATE
ID
COMMENTS
Figure B-7, Loss-on-lgnltlon raw data form.
-------
Appendix B
Revision 0
Date: 8/90
Page 14 of 103
SOIL SAMPLE AIR DRI DETERMINATION
ALL HEIGHTS REPORTED TO 0.01 GRAMS
SAH CODE
TIN
NO.
TIH
wr.
AIR DRY
(TIH+SOIL)
OVEN DRY
(TIN+SOIL)
DATE
ID
COMMENTS
Figure B-8. Air-dry moisture raw data form.
-------
Appendix B
Revision 0
Date: 8/90
Page 15 of 103
Form # 1
Batch #
Submission #
Run #
Re-Analysis _
Parameter - MOIST
Air Dry Moisture Percent
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
1
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37'
38
39
40
41
42
B
Air Dried
Sample
Wt. (g)
XX. XX
c
Oven Dried
Sample
Wt. (g)
XX. XX
D
Calculated
Result
(%)
XX. XX
Figure B-9. Form 1, air-dry moisture parameter data.
-------
Appendix B
Revision 0
Date: 8/90
Page 16 of 103
Form # QC- 1
Batch #
Submission #
Run #
Re-Analysis _
Parameter - MOIST
Air Dry Moisture Percent
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
A
Samp.
#
B
Air Dried
Sample
Wt. (g)
XX. XX
c
Oven Dried
Sample
Wt. (g)
XX. XX
D
Calculated
Result
(%)
XX. XX
E
SD
or
%RSD
XXX. XX
Figure B-10. Form QC-1, quality control data for air-dry moisture content.
-------
Appendix B
Revision 0
Date: 8/90
Page 17 of 103
Form # 2
Submission #
Run #
Re-Analysis
Particle Size Parameters
(Raw Data)
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBK1
B
Air
Dry
Samp.
Wt.
(g)
XX. XX
xxxxxx
= =S=SE=^!=
c
Treat.
Oven
Dry
Wt.
(g)
x.xx
XXXXXX
D
Total
Sand
Wt.
(g)
x.xx
xxxxxx
E
Sand
Very
Coarse
Wt.
(g)
x.xx
XXXXXX
F
Sand
Coarse
Wt.
(g)
x.xx
xxxxxx
G
Sand
Med.
Wt.
(g)
x.xx
xxxxxx
H
Sand
Fine
Wt.
(g)
x.xx
XXXXXX
I
Sand
Very
Fine
Wt.
(g)
x.xx
XXXXXX
J
Pipet
Fine
Silt
+ Clay
Wt. (g)
X . XXXX
K
Pipet
Clay
Wt.
(g)
x.xxxx
XXXXXXXX
Figure B-11. Form 2, particle size parameters (raw data).
-------
Form # 3
Submission #
Orig. Analysis
Re-Analysis
Re-submission
Partical Size Parameters
(Calculated Data)
Appendix B
Revision 0
Date: 8/90
Page 18 of 103
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
2S3S=SSasa
A
Samp.
*
1
2
3
4
5
6
7
3
9
10
11
12
13
14
15
16
17
IS
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
B
Sand
(wt.%)
XX. X
C
silt
(Wt.%)
XX. X
D
Clay
(wt.%)
XX. X
E
Sand
Very
Coarse
(wt.%)
XX. X
F
Sand
Coarse
(wt.%)
XX. X
G
Sand
Medium
(Wt.%)
XX. X
H
Sand
Fine
(wt.%)
XX. X
======
I
Sand
Very
Fine
(wt.%)
XX. X
J
Silt
Coarse
(wt.%.)
XX. X
K
Silt
Fine
(wt.%)
XX. X
Figure B-12. Form 3, particle size parameters (calculated data).
-------
Appendix B
Revision 0
Date: 8/90
Page 19 of 103
Form # QC-2
Submission #
Orig. Analysis
Re-Analysis
Re-submission #
Partical Size Parameters
(Raw Data)
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
=====
Rep]
A
Samp
I
Used
XX
ASKOLS
Licates
B | C
Air (Treat.
Dry | Oven
I Dry
wt. | wt.
(g) I (g)
xx.xxj xx. x
I
I
D
Total
Sand
wt.
(g)
x.xx
E | F
Sand | Sand
Very j Coarse
Coarse)
wt . | wt .
(g) I (g)
x.xx | x.xx
I
I
G
Sand
Medium
wt.
(g)
x.xx
H
Sand
Fine
wt.
(g)
x.xx
I
Sand
Very
Fine
wt.
(g)
x.xx
J
Pipet
Fine
Silt
+ Clay
wt. (g)
x.xxxx
K
Pipet
Clay
wt.
(g)
x.xxxx
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS
QCCS 6
QCCS 7
QCCS 8
B
Air
Dry
wt.
(g)
XX. XX
C
Treat.
Oven
Dry
wt.
(g)
x.xx
D
Sand
Very
Coarse
wt.
(g)
x.xx
E
Sand
Coarse
wt.
(g)
x.xx
F
Sand
Medium
wt.
(g)
x.xx
G
Sand
Fine
wt.
(g)
x.xx
H
Sand
Very
Fine
wt.
(g)
x.xx
I
Pipet
Fine
Silt
+ Clay
wt. (g)
x.xxxx
J
Pipet
Clay
wt.
(g)
x.xxxx
Figure B-13. Form QC-2, quality control for particle tlze parameter* (raw data).
-------
Appendix B
Revision 0
Date: 8/90
Page 20 of 103
Form # QC-3
Submission #
orig. Analysis
Re-Analysis
Re-submission #
Partical Size Parameters
(Calculated Data)
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
A
I
Samp.
#
Used
XX
B
Sand
(wt.%)
XX. X
RSD
B
Sand
(%RSD)
XX. XX
=SSSi:B==S
c
Silt
(wt.%)
XX. X
C
Silt
(%RSD)
XX. XX
D | E
_ 1
Clay Sand
Very
Coarse
(wt.%) (wt.%)
XX . X XX . X
I
I
I
D | E
Clay | Sand
| Very
| Coarse
(%RSD) | (%RSO)
XX . XX j XX . XX
I
I
I
F
Sand
Coarse
(wt.%)
XX. X
F
Sand
Coarse
(%RSD)
XX. XX
G
Sand
Medium
(wt.%)
XX. X
G
Sand
Medium
(%RSD)
XX. XX
H
Sand
Fine
(wt.%)
XX. X
H
Sand
Fine
(%RSD)
XX. XX
I
Sand
Very
Fine
(wt.%)
XX. X
I
Sand
Very
Fine
(%RSD)
XX. XX
J
Silt
Coarse
(wt.%)
XX. X
J
Silt
Coarse
(%RSD)
XX. XX
K
Silt
Fine
(wt.%)
XX. X
K
Silt
Fine
(%RSD)
XX. XX
I
| QCCS
I
I
I
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
B
Sand
(wt.%)
XX. X
c
Silt
(wt.%)
XX. X
D
Clay
(wt.%)
XX. X
E
Sand
Very
Coarse
(wt.%)
XX. X
F
Sand
Coarse
(wt.%)
XX. X
G
Sand
Medium
(wt.%)
XX. X
H
Sand
Fine
(wt.%)
XX. X
I J K
Sand Silt | Silt
Very Coarse Fine
Fine
(wt.%) (wt.%) (wt.%)
XX. X XX. X XX. X
Figure B-14. Form QC-3, quality control particle *lze parameter* (calculated data).
-------
Form # 4
Submission #
Orig. Analysis
Re-Analysis
Re-submission
Parameter - PH_H2O
pH in Water
Appendix B
Revision 0
Date: 8/90
Page 21 of 103
Batch #
Lab Code
Date Analysis Started / /
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
*
1
2
B C D |
Sample
Wt.
(g)
XX. X
3 |
4 1
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Solution
Vol.
(raL)
XX. X
1
Result |
(PH)
x.xx
1
30
31
32
33
34
35
36
37
38
39
40
41
1
1
1
42
RBLK1 XXXXXXXX | XXXXXXXXXX | |
Figure B-15. Form 4, pH In water.
-------
Appendix B
Revision 0
Date: 8/90
Page 22 of 103
form # 5
Submission #
Run #
Jte-Analysis
Parameter - PH_01M
pH in 0.01M Calcium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
1
2
•5
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
B C
Sample Solution
Wt. Vol.
(g) (mL)
XX. X XX. X
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
XXXXXXXX | XXXXXXXXXX
D
Result
(PH)
x.xx
1
1
Figure B-16. Form 5, pH In 0.01 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 23 of 103
Form | QC-4
Submission #
Run |
Re-Analysis
Parameter - PH_H2O
pH in Water
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replic
A
Samp.
Used
XX
===s:===
=======
:ates
B
Sample
Wt.
(g)
XX. X
-
c
Solution
Vol.
(mL)
XX. X
==
==
D
__ — _____
Result
(PH)
x.xx
==
~=
rs
E
SD
XXX . XX
QCCS
True
High
LOW
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(PH)
x.xx
Figure B-17. Form QC-4, quality control parameter pH In water.
-------
Appendix B
Revision 0
Date: 8/90
Page 24 of 103
Form # QC-5
Submission #
Run # _
Re-Analysis
Parameter - PH_01M
pH in 0.01M Calcium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replic
A
Samp.
#
Used
XX
:ates
==:=======:=2=
B
Sample
Wt.
(g)
XX. X
c
Solution
Vol.
(mL)
XX. X
============
D
Result
(PH)
x.xx
==
E
SD
XXX. XX
=========
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(PH)
x.xx
Figure B-18. Form QC-5, quality control parameter pH In 0.01 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 25 of 103
Form # 6A Parameter - CEC_OAC Batch »
Cation Exchange Capacity - Ammonium Acetate Lab Code
•(Flow Injection Analysis)
Submission # Date Analysis Started
Orig. Analysis Date Analysis Completed
Re-Analysis Date Form Completed
Re-submission Lab Manager Initials
A
Samp.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
B
Sample
Wt.
(g)
x.xx
c
Final
Soln.
Vol.
(raL)
XX. X
RBLK1| XXXXXXXX |
RBLK2 | XXXXXXXX j
RBLK3 | XXXXXXXX |
D
Aliquot
Vol.
(BL)
XX. X
E
Dilution
Vol.
(mL)
XX. X
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(meq/lOOg)
XXX. XXX
| XXXXXXXXXXXX
| XXXXXXXXXXXX
| XXXXXXXXXXXX
Figure B-19. Form 6A, cation exchange capacity-ammonium acetate (flow Injection analysis).
-------
Appendix B
Revision 0
Date: 8/90
Page 26 of 103
Form I 6B Parameter - CECJDAC Batch *
Cation Exchange Capacity - Ammonium Acetate Lab Code
(Titration Method)
Submission # Date Analysis Started
Oriq. Analysis Date Analysis Completed
Re-Analysis Date Form Completed
Re-submission Lab Manager Initials
A
Samp.
*
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
B
Sample
Wt.
(g)
x.xx
XXXXXXXX
C D|E
Titrant Acid | Calculated
Vol. Normality | Result
1
(mL) N | (meq/lOOg)
XX. XX X.XXXX 1 I XXX. XXX
II
| XXXXXXXXXX | |
| XXXXXXXXXX | 1
| XXXXXXXXXX | 1
| XXXXXXXXXX 1 j
| XXXXXXXXXX | |
I XXXXXXXXXX 1 1
I XXXXXXXXXX I |
1 XXXXXXXXXX 1 I
| XXXXXXXXXX I |
I XXXXXXXXXX 1 1
I XXXXXXXXXX | |
1 XXXXXXXXXX | 1
1 XXXXXXXXXX I |
1 XXXXXXXXXX | |
I XXXXXXXXXX 1 1
j XXXXXXXXXX j 1
1 XXXXXXXXXX | 1
| XXXXXXXXXX | |
I XXXXXXXXXX I 1
I XXXXXXXXXX | |
| XXXXXXXXXX | |
| XXXXXXXXXX | 1
| XXXXXXXXXX | |
I XXXXXXXXXX | 1
| XXXXXXXXXX | |
| XXXXXXXXXX | 1
1 XXXXXXXXXX | |
1 XXXXXXXXXX | |
I XXXXXXXXXX | 1
| XXXXXXXXXX | |
1 XXXXXXXXXX | |
I XXXXXXXXXX | 1
I XXXXXXXXXX | 1
| XXXXXXXXXX f |
I XXXXXXXXXX 1 I
1 XXXXXXXXXX | 1
| XXXXXXXXXX | |
1 XXXXXXXXXX 1 1
1 XXXXXXXXXX | 1
| XXXXXXXXXX 1 j
| XXXXXXXXXX j 1
1 XXXXXXXXXX 1 1
| RBLK2 | XXXXXXXX | j XXXXXXXXXX j j
| RBLK3 | XXXXXXXX | | XXXXXXXXXX | |
Figure B-20. Form 6B, cation exchange capacity-ammonium acetate (titratlon method).
-------
Appendix B
Revision 0
Date: 8/90
Page 27 of 103
Form # 7A Parameter - CEC_CL Batch #
Cation Exchange Capacity - Ammonium Chloride Lab Code
(Flow Injection Analysis)
Submission # Date Analysis Started
Orig. Analysis Date Analysis completed
Re-Analysis ~~ Date Form Completed
Re-submission Lab Manager Initials
A
Samp.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
B
Sample
Wt.
(g)
x.xx
c
Final
Soln.
Vol.
(mL)
XX. X
RBLK1 | XXXXXXXX |
RBLK2 | XXXXXXXX |
|RBLK3| XXXXXXXX |
D
Aliquot
Vol.
(mL)
XX. X
E
Dilution
Vol.
(mL)
XX. X
F
Inst.
Reading
(rag/L)
ixxx . xx
G
Calculated
Result
(meq/lOOg)
XXX . XXX
| XXXXXXXXXXXX
| XXXXXXXXXXXX
1 XXXXXXXXXXXX
Figure B-21. Form 7A, cation exchange capacity-ammonium chloride (flow Injection analysis).
-------
Appendix B
Revision 0
Date: 8/90
Page 28 of 103
Form # 7B
Submission I
Orig. Analysis
Re-Analysis
Re-submission
Parameter - CEC_CL Batch #
Cation Exchange Capacity - Ammonium Chloride Lab Code
(Titration Method)
Date Analysis Started /
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
*
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
B
Sample
Wt.
(g)
x.xx
C 1 D |
Titrant | Acid |
Vol. | Normality |
(raL) | N |
XX. XX j X.XXXX j
1 1
| XXXXXXXXXX | |
1 XXXXXXXXXX | j
I XXXXXXXXXX | |
| XXXXXXXXXX I |
| XXXXXXXXXX | 1
j XXXXXXXXXX 1 1
1 XXXXXXXXXX | 1
I XXXXXXXXXX | 1
| XXXXXXXXXX | 1
| XXXXXXXXXX | |
| XXXXXXXXXX | |
1 XXXXXXXXXX 1 1
I XXXXXXXXXX | |
1 XXXXXXXXXX | |
1 XXXXXXXXXX | |
I XXXXXXXXXX I |
I XXXXXXXXXX I |
I XXXXXXXXXX | |
| XXXXXXXXXX 1 1
I XXXXXXXXXX | |
| XXXXXXXXXX | |
| XXXXXXXXXX |
I XXXXXXXXXX | |
| XXXXXXXXXX | |
| XXXXXXXXXX | |
| XXXXXXXXXX | |
| XXXXXXXXXX | |
| XXXXXXXXXX | |
I XXXXXXXXXX | 1
| XXXXXXXXXX I |
| XXXXXXXXXX | |
| XXXXXXXXXX | |
| XXXXXXXXXX | |
I XXXXXXXXXX |
| XXXXXXXXXX |
1 XXXXXXXXXX |
| XXXXXXXXXX |
| XXXXXXXXXX |
| XXXXXXXXXX | |
I XXXXXXXXXX | |
j XXXXXXXXXX |
RBLK1 | XXXXXXXX \ j XXXXXXXXXX
RBLK2 | XXXXXXXX | | XXXXXXXXXX |
RBLK3 | XXXXXXXX | | XXXXXXXXXX |
E
Calculated
Result
(meq/lOOg)
XXX. XXX
Figure B-22. Form 7B, cation exchange capacity-ammonium chloride (titratlon method).
-------
Appendix B
Revision 0
Date: 8/90
Page 29 of 103
Form # QC-6A Parameter - CEC OAC Batch *
Cation Exchangable Capacity In Ammonium Acetate Lab Code
(Flow Injection Analysis)
Submission # Date Analysis Started
orig. Analysis Date Analysis Completed
Re-Analysis Date Form Completed
Re-submission # Lab Manager Initials
Replicates
A | B
Samp. | Sample
# I wt.
Used j
I (g)
XX | X . XX
c
Final
Soln.
Vol.
(mL)
XX. X
I I
I
I
Matrix Spikes
A | B
j
Samp. | Sample
# | Allq.
Used | Vol.
I (nL)
XX | XX . X
I
I
I
•3KxaM»MMa
» ,,
spike |
Added |
(mL) |
XX. X |
_ J_
I
I
D|E | F |
G | H
Aliquot | Dilution | Inst. |Calculated|
Vol. | Vol. | Reading | Result | RSD
I I I I
(mL) | (mL) | (mg/L) | (meq/lOOg) | (%)
XX. X | XX. X | XXX. XX | XXX. XXX | XXX. XX
I I I
I I I
I I I
D " E | F || G
Dilut. | | Inst.
Spike Vol . | Vol . | | Reading
Added | | |
(mg/L) (mL) | (mL) | | (mg/L)
XXXX.X XX. X | XX. X | | XXX. XX
I I II
I I II
I I II
I
I
II
H
Spike
j Recovery
(*)
XXX . XX
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg/L)
XXX . XX
DL-QCCS
True
High
Low
Meas.
(mg/L) |
XXX . XX |
1
1
Calibration
Blank
Inst.
Reading
(mg/L)
XXX.XX
Figure B-23. Form OC-6A, quality control parameter cation exchangeable capacity-ammonium
acetate (flow Injection analysis).
-------
Appendix B
Revision 0
Date: 8/90
Page 30 of 103
Form # QC-6B
Submission I
Orig. Analysis
Re-Analysis
Re-submission #
Parameter - CEC_OAC Batch #
Cation Exchange Capacity in Ammonium Acetate Lab Code
(Titration Method)
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
A B C D | E | | F
!____________I ________
Calculated |
t Wt. Vol. Normality) Results j RSD
Used | |
(g) (mL) N | (meq/lOOg) | (%)
XX X.XX XX.XX X.XXXX I XXX.XXX j j XXX.XX
I I
I I
Matrix Spikes
A | B | C D | E | F G
-----j_______|________ ______—_i__________j __—_____ __________
Samp.| Vol. | Cone. Titrant | Acid | Calc. Spike
# | Spike j Spike Vol. j Normality| Results Recovery
j Added I Added | |
| (mL) | (meq) (mL) | N | (meq) (%)
XX | X.XX I XX.XXX XX.XX I X.XXXX I XXX.XXX XXX.XX
I I I I II II
QCCS I (meq) | DL-QCCS (meq) | Calibration
I xxx.xxx I xxx.xxx I Blank
True | j True | Inst.
High | | High | Reading
Low j I Low j (raeq)
QCCS 1 I | Meas. j xxx.xxx
QCCS 2 I
QCCS 3 I
QCCS 4 I
QCCS 5 I
QCCS 6 j
QCCS 7 I
QCCS 8 |
Figure B-24. Form QC-6B, quality control parameter cation exchangeable capacity-ammonium
acetate (tltratlon method).
-------
Appendix B
Revision 0
Date: 8/90
Page 31 of 103
Form # QC-7A Parameter - CEC CL Batch #
Cation Exchangable Capacity Tn Ammonium Chloride Lab Code
(Flow Injection Analysis)
Submission # Date Analysis Started
orig. Analysis Date Analysis Completed
Re-Analysis Date Form Completed
Re-submission # Lab Manager Initials
| Replicates
A
Samp.
Used
XX
B
Sample
Wt.
(g)
x.xx
C | D
Final | Aliquot
Soln. j Vol.
Vol. |
(mL) | (mL)
XX. X | XX. X
1
1
1
E 1
Dilution |
vol. |
1
XX. X |
1
1
1
F
Inst,
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(meq/lOOg)
XXX. XXX
H
RSD
(%)
XXX. XX
Matrij
A
Samp.
*
Used
XX
c Spikes
a | c
Sample | Vol.
Aliq. | Spike
Vol. | Added
(mL) | (mL)
XX. X | XX. X
I
I
I
D
cone.
Spike
Added
(mg/L)
xxxx.x
I
I
I
E | F
Aliq. | Dilut.
Vol . | Vol .
I
(mL) | (BL)
XX. X | XX. X
I
I
I
G || H
Inst. | | Spike
Reading \ (Recovery
(mg/L) || (*)
XXX. XX I j XXX. XX
II
II
II
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg/L) |
XXX. XX |
*™"™™"™™™ 1
1
1
1
1
1
1
1
1
1
1
DL-QCCS
True
High
Low
Meas.
(rag/L)
XXX.XX
Calibration
Blank
Inst.
Reading
(mg/L)
XXX.XX
Figure B-25. Form QC-7A, quality control parameter cation exchangeable capacity-ammonium
chloride (flow Injection analysis).
-------
Appendix B
Revision 0
Date: 8/90
Page 32 of 103
Form # QC-7B
Submission I
Orig. Analysis
Re-Analysis
Re-submission #
Batch
Lab Code
Parameter - CEC CL
Cation Exchange Capacity - Xmmonium Chloride
(Titration Method)
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
A
Samp.
• Used
XX
B
Sample
Wt.
(g)
x.xx
c
Titrant
Vol.
(mL)
XX. XX
0 || E
Acid | | Calculated
Normality | | Results
I I
N | | (meq/lOOg)
x.xxxx I I xxx. xxx
1 1
II
II
F
RSD
(*)
XXX . XX
Matrix Spike:
A | B
Samp. | Vol.
# I Spike
| Added
1 (mL)
XX | X . XX
1
1
1
3
C
Cone.
Spike
Added
(meq)
XX . XXX
D
Titrant
Vol.
(mL)
XX. XX
E
Acid
Normality
N
X . XXXX
F
Calc.
Results
(meq)
xxx . xxx
G
Spike
Recovery
(*)
XXX . XX
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(meq)
XXX . XXX
DL-QCCS
True
High
Low
Meas.
(raeq)
xxx. xxx
Calibration
Blank
Inst.
Reading
(meq)
xxx . xxx
Figure B-26. Form QC-7B, quality control parameter cation exchangeable capacity-ammonium
chloride (tltratlon method).
-------
Appendix B
Revision 0
Date: 8/90
Page 33 of 103
Form t 8
Submission If
Orig. Analysis
Re-Analysis
Re-submission
Parameter - CA_OAC
Calcium in Anunonium Acetate
Batch
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A B
Samp.
I
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
Sample
Wt.
(g)
x.xx
c
Final
Soln.
Vol.
(mL)
XX. X
RBLK1|XXXXXXXX|
RBLK2 | XXXXXXXX |
RBLK3|XXXXXXXX|
D E
Aliquot Dilution
Vol. Vol.
(mL) (ML)
XX. X
XX. X
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(meq/lOOg)
XXX. XXX
IXXXXXXXXXXXXI
IXXXXXXXXXXXXI
IXXXXXXXXXXXXI
Figure B-27. Form 8, calcium In ammonium acetate.
-------
Appendix B
Revision 0
Date: 8/90
Page 34 of 103
Form # 9
Submission #
Orig. Analysis
Re-Analysis
Re-submission
Parameter - MG_OAC
Magnesium in Ammonium Acetate
Batch *
Lab Code
Date Analysis Started
Date Analysis Completed \
Date Form Completed
Lab Manager Initials
A
| Samp.
ft
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
B
Sample
Wt.
(g)
x.xx
c
Final
Soln.
Vol.
(mL)
XX. X
RBLK1|XXXXXXXX|
RBLK2 | XXXXXXXX |
RBLK3 | XXXXXXXX |
D
Aliquot
Vol.
(raL)
XX. X
E
Dilution
Vol.
(mL)
XX. X
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(meq/lOOg)
XXX. XXX
|XXXXXXXXXXXX|
jxxxxxxxxxxxxi
| XXXXXXXXXXXX |
Figure B-28. Form 9, magnesium In ammonium acetate.
-------
Appendix B
Revision 0
Date: 8/90
Page 35 of 103
Form # 10
Submission # —
orig. Analysis
Re-Analysis —
Batch #
Lab Code
Parameter - KJ3AC
Potassium in Ammonium Acetate
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
MXSKSS
A B
SampT "sample
| ' Wt.
x-**__ =
1
2
3
4
5
6
7
8
9
10 I
11
12 I
13
14
15
16
17
18 I
19 I
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
VMK3B W
£
Final
Soln.
Vol.
(mL)
XX. X
mmmmxaamm
'-—"—"•-• E ) F 1 G !
— — — — — — — — — — — — — — — — — Tn«t* 1
Alicniot Dilution msy • i
voi Vol « 1 Rosclincf 1
(mL) (mD
-------
Appendix B
Revision 0
Date: 8/90
Page 36 of 103
Form | 11
Submission #
Orig. Analysis
Re-Analysis
Re-submission
Parameter - NA_OAC
Sodium in Ammonium Acetate
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
awmK
A
|Samp.
1
2
3
4
5
6
7
B
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
B
Sample
Wt.
(g)
x.xx
c
Final
Soln.
Vol.
(mL)
XX. X
RBLK1|XXXXXXXX|
RBLK2 JXXXXXXXXJ
RBLK3 | XXXXXXXX j
D
Aliquot
Vol.
(ML)
XX. X
E
Dilution
Vol.
(mL)
XX. X
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(meq/lOOg)
XXX. XXX
|XXXXXXXXXXXX|
j xxxxxxxxxxxx i
|XXXXXXXXXXXX|
Figure B-30. Form 11, sodium In ammonium acetate.
-------
Appendix B
Revision 0
Date: 8/90
Page 37 of 103
Form # QC-8 Parameter - CA OAC
Calcium in Ammonium Acetate
Batch *
Lab Code
Submission f Date Analysis Started / /
Drig. Analysis Date Analysis Completed / /
te-Analysis Date Form Completed / /
Re-submission # Lab Manager Initials
Replicates
A B | C D
Final Aliquot
f Wt. | Soln. Vol.
Used | Vol.
(g) | (mL) (mL)
XX X.XX | XX. X XX. X
1 1 1
1 1
1 1 1
E F
Dilution Inst.
| Vol . Reading
(mL) (mg/L)
XX . X XXX . XX
1
1
G H
Calculated
Result . RSD
(meq/lOOg) (%)
XXX . XXX XXX . XX
1
II
II
Matri:
A
Samp.
*
Used
XX
« Spikes
B
-------
Sample
Aliq.
Vol.
(mL)
XX. X
C | D|E
Vol. | Cone. | Aliq.
Spike | Spike | Vol.
Added j Added |
(mL) | (mg/L) | (mL)
XX. X | XXXX.X | XX. X
I I
I I
I I
F
Dilut.
Vol.
(mL)
XX. X
G
Inst.
Reading
(mg/L)
XXX . XX
H
Spike
Recovery
(*)
XXX . XX
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg/L)
XXX. XX
| DL-QCCS
«»«.»..,
| True
| High
| Low
I Meas.
«»»»«mma=
| (mg/L) |
| XXX. XX |
1 1
1 1
1 1
1 1
Calibration
Blank
Inst.
Reading
(mg/L)
XXX.XX
Figure B-31. Form QC-8, quality control calcium In ammonium acetate.
-------
Appendix B
Revision 0
Date: 8/90
Page 38 of 103
Form 1 QC-9
Submission 1
Drig. Analysis
le-Analysis
Re-submission #
Me
Parameter - KG OAC
Batch I
ignesium in Ammonium Acetate Lao code
Date Analysis Started / /
Date Analysis Completed / /
Date Form Completed / /
Lab Manager Initials
Replicates
A | B
Sample
# 1 wt.
Used j
1 (g)
XX | X . XX
1
1
1
Matrix Spikes
*~~A "|" B
Samp. | Sample
1 1 Allq.
Used I Vol.
I (n>L)
XX | XX. X
1
1
1
C
Final
Soln.
Vol.
(mL)
XX. X
••mmmm
I 0 | E
| Aliquot | Dilution
I Vol. | Vol.
1 1
I (mL) | (mL)
| XX. X | XX. X
1 1
1 1
1 1 1
c
vol.
Spike
Added
(mL)
XX. X
B««M«W»Ma
D|E F
Cone. | Aliq. Dilu
Spike | Vol. Vol
Added |
(mg/L) | (mL) (mL
XXXX.X | XX. X XX.
1
1
1
F G H
Inst. Calculated
Reading Result RSD
(mg/L) (meq/lOOg) (%)
XXX. XX XXX. XXX XXX. XX
1 1
"" M
1 II
G H
t. Inst. Spike
Reading Recovery
) (mg/L) (I)
X XXX . XX XXX . XX
II
1
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg/L)
XXX . XX
1
DL-QCCS | (mg/L)
XXX.XX
True
High
Low
Meas.
Calibration
Blank
Inst.
Reading
(mg/L)
XXX. XX
Figure B-32. Form QC-9, quality control magnesium In ammonium acetate.
-------
Appendix B
Revision 0
Date: 8/90
Page 39 of 103
Form # QC-10 Parameter - K OAC
Potassium in Ammonium Ace
Submission #
Orig. Analysis
Re-Analysis
Re-submission #
Batch *
:ate Lab Code
Date Analysis Started / /
Date Analysis Completed / /
Date Form Completed / /
Lab Manager Initials
Replicates
A I
£
# 1
Used |
XX |
BCD E
ample Final Aliquot Dilution
Wt. Soln. Vol. Vol.
Vol.
(g) (mL) (mL) (mL)
X.XX XX. X XX. X XX. X
F G H
Inst. Calculated
Reading Result RSD
(mg/L) (meq/lOOg) (%)
XXX . XX XXX . XXX XXX . XX
1 1
1
1
1 1
1 1
Matrix Spikes
A
Samp. £
Used
XX |
........
B C | D E F
G H
ample Vol. | Cone. Aliq. Dilut. Inst. Spike
Aliq. Spike | Spike Vol. Vol. Reading Recovery
Vol. Added j Added
(mL) (mL) | (mg/L) (mL) (mL) (mg/L) (%)
XX. X XX. X j XXXX.X XX. X XX. X XXX. XX XXX. XX
1 1 1
1 1
1 1 I
T T T i
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg/L) DL-QCCS (mg/L)
XXX. XX XXX. XX
True
High
| Low
| Meas.
Calibration
Blank
Inst.
Reading
(mg/L)
XXX . XX
Figure B-33. Form QC-10, quality control potassium In ammonium acetate.
-------
Appendix B
Revision 0
Date: 8/90
Page 40 of 103
Form ft QC-11
Submission #
orig. Analysis
Re-Analysis
Re-submission #
Parameter - NA_OAC
Sodium in Ammonium Acetate
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
*
Samp.
Used
XX
B
Sample
Wt.
(g)
x.xx
c
Final
soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. X
E
Dilution
Vol.
(mL)
XX. X
F 1
Inst. |
Reading |
1
(mg/L) |
XXX . XX |
!
1
1
G I
|
Calculated]
Result |
' 1
(meq/lOOg) |
XXX. XXX |
1
1
1
H
RSD
XXX. XX
Matri:
A
Samp.
ft
Used
XX
c Spikes
B
Sample
Allq.
Vol.
(mL)
XX. X
C | D
Vol. | Cone.
spike | Spike
Added | Added
(mL) | (mg/L)
XX . X | XXXX . X
1 1
1 1
1 1
E | F
Aliq. | Dilut.
Vol . | Vol .
1
(mL) | (mL)
XX. X | XX. X
1
1
1
G
Inst.
Reading
(mg/L)
XXX . XX
H
Spike
Recovery
(*)
XXX . XX
QCCS
True
High
Low
QCCS 1
QCCS 3
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(rag/L)
XXX . XX
| DL-QCCS
| True
| High
| Low
| Meas.
(mg/L)
XXX. XX
Calibration
Blank
Inst.
Reading
(mg/L)
XXX . XX
Figure B-34. Form QC-11, quality control sodium In ammonium acetate.
-------
Appendix B
Revision 0
Date: 8/90
Page 41 of 103
Form # 12
Submission #
Orig. Analysis
Re-Analysis
Re-submission
Parameter - CA_CL
Calcium in Ammonium Chloride
Batch *
Lab code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
*
1
2
3
4
5
6
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
B
Sample
Wt.
(g)
x.xx
c
Final
Soln.
Vol.
(aL)
XX. X
RBLK1 | XXXXXXXX |
RBLK2|XXXXXXXX|
RBLK3 I XXXXXXXX |
D
Aliquot
Vol.
(mL)
XX. X
E
Dilution
Vol.
(mL)
XX. X
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(meq/lOOg)
XXX . XXX
| XXXXXXXXXXXX |
|XXXXXXXXXXXX|
1 XXXXXXXXXXXX |
Figure B-35. Form 12, calcium In ammonium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 42 of 103
Form # 13
Submission #
Orig. Analysis
Re-Analysis
Re-submission
Parameter - MG_CL
Magnesium in Ammonium Chloride
Batch *
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
B
Sample
Wt.
(g)
x.xx
41 |
42 |
| RBLK1 | XXXXXXXX
| RBLK2 | XXXXXXXX
| RBLK3 | XXXXXXXX
c
Final
Soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. X
E
Dilution
Vol.
(mL)
XX. X
F
Inst.
Reading
(rag/L)
XXX. XX
G
Calculated
Result
(meq/lOOg)
XXX. XXX
| XXXXXXXXXXXX
| XXXXXXXXXXXX
| XXXXXXXXXXXX
Figure B-36. Form 13, magnesium In ammonium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 43 of 103
Form * 14
Submission #
Orig. Analysis
Re-Analysis
Re-submission
Parameter - K_CL
Potassium in Ammonium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
sam^a
A
Samp.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
B
Sample
Wt.
(g)
x.xx
17 I
18
19 |
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
c
Final
Soln.
Vol.
(mL)
XX. X
| RBLK1 | XXXXXXXX |
| RBLK2 | XXXXXXXX |
j RBLK3 1 XXXXXXXX I
D
_________
Aliquot
Vol.
(mL)
XX. X
E
Dilution
Vol.
(fflL)
XX. X
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(meg/lOOg)
XXX . XXX
I xxxxxxxxxxxx
I xxxxxxxxxxxx
1 xxxxxxxxxxxx
Figure B-37. Form 14, potassium In ammonium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 44 of 103
Form | 15
Submission I
Orig. Analysis
Re-Analysis
Re-gubmlssion
Parameter - NA_CL
Sodium in Ammonium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
I
I
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
B
Sample
Wt.
(g)
x.xx
c
Final
Soln.
Vol.
(mL)
XX. X
I RBLK1 | XXXXXXXX |
| RBLK2 | XXXXXXXX |
| RBLK3 | XXXXXXXX |
D
Aliquot
Vol.
(mL)
XX. X
c
Dilution
Vol.
(mL)
XX. X
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(meq/lOOg)
XXX . XXX
I xxxxxxxxxxxx
1 xxxxxxxxxxxx
| XXXXXXXXXXXX i
Figure B-38. Form 15, sodium In ammonium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 45 of 103
Form # 16
Submission I
orig. Analysis
Re-Analysis
Re-submission
Parameter - AL_CL
Aluminum in Ammonium Chloride
Batch *
Lab Code
Date Analysis Started
Date Analysis Completed ,
Date Form Completed
Lab Manager Initials
A
Samp.
*
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
B
Sample
Wt.
(g)
x.xx
c
Final
Soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. X
1
1
RBLK1|XXXXXXXX|
RBLK2 | XXXXXXXX j
RBLK3 | XXXXXXXX j
E
Dilution
Vol.
(mL)
XX. X
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(meq/lOOg)
XXX. XXX
|XXXXXXXXXXXX|
1 xxxxxxxxxxxx i
| XXXXXXXXXXXX |
Figure B-39. Form 16, aluminum In ammonium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 46 of 103
Fora # QC-12
Submission #
Orig. Analysis
Re-Analysis
Re-submission f
Parameter - CA CL
Calcium in Ammonium Chloride
Batch »
Lab Code
Date Analysis Started
Date Analysis completed
Date Form Completed
Lab Manager Initials
Replic
A
Samp.
*
Used
XX
:ates
B ! C
________
Sample | Final
Wt. I Soln.
j vol.
(g) | (mL)
x.xx 1 xx. x
1
1
1
D
Aliquot
vol.
(BL)
XX. X
E I
Vol. |
(mL) 1
XX. X I
1
1
1
F 1 1 G 1
Inst. | (Calculated |
Reading I j Result I
1 1 1
(rag/L) | | (meq/lOOg) |
XXX. XX 1 | XXX. XXX 1
II 1
II 1
II 1
H
--------
RSD
(%)
XXX . XX
Matrix i
A I
Samp. | !
# 1
Used j
XX j
1
1
1
QCCS
True
High
Low
QCCS 1
QCCS 3
QCCS 5
QCCS 6
QCCS 7
QCCS 8
Spikes
B
Sample
Aliq. i
Vol. 1
(mL)
XX. X
(mg/L)
XXX. XX
B»MWM_!««IV
C D | E | F G H
Vol. Cone. | Aliq. | Dilut. Inst. Spike
Spike spike j Vol. j Vol. Reading Recovery
Vdded Added j j
(mL) (mg/L) | (mL) | (mL) (mg/L) (»)
XX. X XXXX.X 1 XX. X | XX. X XXX. XX XXX. XX
1 1
1 1 1
III 1
I DL-QCCS (mg/L) | Calibration
j xxx. xx | Blank
| True | Inst.
| High | Reading
1 Low | (mg/L)
1 Meas. | xxx. xx
i
Figure B-40. Form QC-12, quality control calcium In ammonium chlorldo.
-------
Appendix B
Revision 0
Date: 8/90
Page 47 of 103
Form # QC-13
Submission I
Orig. Analysis
Re-Analysis
Re-submission #
Parameter - MG_CL
Magnesium in Ammonium chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replii
A
Samp.
Used
XX
:ates
B
Sample
Wt.
(9)
x.xx
c
Final
soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. X
E
Dilution
vol.
(mL)
XX. X
Inst. |
Reading |
1
XXX . XX |
1
1
1
G
Calculated
Result
(meq/lOOg)
XXX. XXX
1
H
RSD
(*)
XXX . XX
1
Matrix Spikes
A
Samp.
w
Used
XX
B
Sample
Allq.
Vol.
(mL)
XX. X
c
vol.
Spike
Added
(mL)
xx. x
D | E
Aliq.
Spike | Vol.
Added |
(rag/L) | (mL)
XXXX .X | XX . X
F
Dilut.
Vol.
(mL)
XX. X
G
Inst.
Reading
(mg/L)
XXX . XX
H
Spike
Recovery
(%)
XXX . XX
MMOEaiwtaiMasxsaeai
II
II
tatBi
11
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg/L)
XXX. XX
DL-QCCS
True
High
Low
Meaa.
(mg/L)
XXX.XX
Calibration
Blank
Inst.
Reading
(mg/L)
XXX.XX
Figure B-41. Form QC-13, quality control magnesium In ammonium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 48 of 103
Fora # QC-14
Submission #
Orig. Analysis
Re-Analysis
Re-submission i
Parameter - K_CL
Potassium in Ammonium Chloride
Batch
-------
Appendix B
Revision 0
Date: 8/90
Page 49 of 103
Form # QC-15
Submission I
Orig. Analysis
Re-Analysis
Re-submission #
Parameter - NA CL
Sodium in Ammonium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
A | B
~ -----
Sample
# I Wt.
Used |
1 (g)
XX | X . XX
1
1
1
c
Final
Soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. X
E
Dilution
Vol.
(mL)
XX. X
F
inst.
Reading
(mg/L)
XXX. XX
1 G
(Calculated
I Result
1
| (meq/lOOg)
| XXX. XXX
1
1 1
1 1
H
RSD
(*)
XXX. XX
1
Matrix Spikes
A
Samp.
Used
XX
B
Sample
Aliq.
Vol.
(mL)
XX. X
C | D
Vol. | Cone.
Spike j Spike
Added | Added
(mL) | (mg/L)
XX . X | XXXX . X
E | F
Aliq. | Dilut.
Vol . | Vol .
1
(mL) | (mL)
XX . X | XX . X
1 G
| Inst.
j Reading
1 (mg/D
| XXX. XX
1 H
| Spike
1 Recovery
! (%,
| XXX . XX
1
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg/L)"
XXX. XX
DL-QCCS
True |
High I
Low |
Meas. |
(mg/L)
XXX.XX
Calibration
Blank
Inst.
Reading
(mg/L)
XXX.XX
Figure B-43. Form QC-15, quality control sodium In ammonium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 50 of 103
Form # QC-16
Submission #
Orig. Analysis
Re-Analysis
Re-submission I
Parameter - AL_CL
Aluminum in Ammonium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Repli<
A
Samp.
#
Used
XX
:ates
B
Sample
Wt.
(g)
x.xx
c
Final
Soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. X
E
Dilution
Vol.
(mL)
XX. X
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(meq/lOOg)
XXX . XXX
H
RSD
(*)
XXX. XX
Matri)
A
Samp.
#
Used
XX
c Spikes
B
Sample
Allq.
Vol.
(mL)
XX. X
c
Vol.
Spike
Added
(mL)
XX. X
D
Cone.
Spike
Added
(mg/L)
XXXX . X
1
1
1
E
Aliq.
Vol.
(mL)
XX. X
F
DilUt.
vol.
(mL)
XX. X
G
Inst.
Reading
(mg/L)
XXX . XX
H
Spike
Recovery
(%)
XXX . XX
QCCS
True
High
Low
QCCS 1
i n •* in v> r- eo
o co co co co co co
JUCJCJOUCJ
JCJCJU UUU
yacxycyoicy
(mg/L)
XXX . XX
DL-QCCS
True
High
Low
Meas.
(mg/L)
XXX . XX
Calibration
Blank
Inst.
Reading
(mg/L)
XXX . XX
.............
Figure B-44. Form QC-16, quality control aluminum In ammonium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 51 of 103
Form # 18
Submission #
Run #
Re-Analysis
Parameter - PH_002M
pH in 0.002M Calcium Chloride
Batch *
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A B
Samp. Sample
# wt.
(g)
XX. X
1
2
3
C
Solution
Vol.
(mL)
XX. X
D
Result
(pH)
x.xx
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37 |
38
39
40
41
42
RBLKl | XXXXXXXX
XXXXXXXXXX |
Figure B-45. Form 18, pH In 0.002 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 52 of 103
Form # 19
Submission #
Run #
Re-Analysis
Parameter - CA_CL2
Calcium in Calcium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
1
2
3
4
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK2
RBLK3
B
Sample
Wt.
(g)
XX. XX
XXXXXXXX
xxxxxxxx
XXXXXXXX
c
Initial
Soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. XX
E
Total
Diluted
Vol.
(mL)
xxx. xx
F
Inst.
Reading
(mg/L)
XXX. XX
G
Calculated
Result
(meq/lOOg)
xxx . xxx
XXXXXXXXXXXX |
xxxxxxxxxxxx i
XXXXXXXXXXXX
Figure B-46. Form 19, calcium In 0.002 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 53 of 103
Form # 20
Submission #
Run #
Re-Analysis
Parameter - MG_CL2
Magnesium in Calcium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
—————
Samp.
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK2
RBLK3
B
Sample
Wt.
(g)
XX. XX
XXXXXXXX
xxxxxxxx
XXXXXXXX
c
Initial
Soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
F
Inst.
Reading
(mg/L)
XXX. XX
G
Calculated
Result
(meq/lOOg)
XXX . XXX
1
XXXXXXXXXXXX
XXXXXXXXXXXX |
XXXXXXXXXXXX
Figure B-47. Form 20, magnesium In 0.002 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 54 of 103
Form #21
Submission #
Run #
Re-Analysis
Parameter - K_CL2
Potassium in Calcium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
=S^=5SSS^=
A
Samp.
*
B
Sample
Wt.
(g)
XX. XX
1
2
3
4
5
6
7
3
9
10
11
1 12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
c
Initial
Soln.
D
Aliquot
Vol.
Vol.
(mL) (mL)
XX . X XX . XX
E 1 F
Total
Diluted
Vol.
(mL)
XXX . XX
Inst.
Reading
(mg/L)
xxx . xx
1
1
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1 | XXXXXXXX
RBLK2 | XXXXXXXX |
RBLK3 | XXXXXXXX j
— ~— • — -•—•—— ———.-—— — —.——.— — —
==========::
= ==2==^=£^=±^==
1
- ... ...... — - .- i - -_.— .-i .. —
1 G
Calculated
Result
(meq/lOOg)
XXX . XXX
j
XXXXXXXXXXXX
xxxxxxxxxxxx
XXXXXXXXXXXX
Figure B-48. Form 21, potassium In 0.002 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 55 of 103
Form # 22
Submission #
Run #
Re-Analysis
Parameter - NA_CL2
Sodium in Calcium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK?
RBLK3
B
Sample
Wt.
(g)
XX. XX
XXXXXXXX
xxxxxxxx
XXXXXXXX |
c
Initial
Soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
F |
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(meq/lOOg)
XXX . XXX
XXXXXXXXXXXX
xxxxxxxxxxxx
| XXXXXXXXXXXX
Figure B-49. Form 22, sodium In 0.002 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 56 of 103
Form # 23
Submission #
Run #
Re-Analysis
Parameter - FE CL2
Iron in Calcium cHloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Samp.
B
Sample Initial Aliquot
Wt. | Soln. Vol.
| Vol.
(g) I (mL) (mL)
XX.XX I XX.X XX.XX
i !
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
:=s==:=s= I =:====:===
RBLK1|XXXXXXXX
RBLK2|XXXXXXXX
RBLK3|XXXXXXXX
Total
Diluted
Vol.
(mL)
XXX.XX
Inst.
Reading
(mg/L)
XXX.XX
Calculated
Result
(meg/lOOg)
XXX.XXX
XXXXXXXXXXXX
xxxxxxxxxxxx
XXXXXXXXXXXX
Figure B-50. Form 23, Iron In 0.002 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 57 of 103
*orm # 24
Parameter - AL_CL2
Aluminum in Calcium Chloride
Batch i
Lab Code
5ubmission #
*un #
^e-Analysis
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK2
RBLK3
B
Sample
Wt.
(g)
XX. XX
XXXXXXXX
XXXXXXXX
XXXXXXXX
c
Initial
Soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
1
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(meq/lOOg)
XXX. XXX
1
1
XXXXXXXXXXXX
xxxxxxxxxxxx
XXXXXXXXXXXX
Figure B-51. Form 24, aluminum In 0.002 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 58 of 103
Form # QC-18
Submission #
Run #
Re-Analysis
Parameter - PH_002M
pH in 0.002M Calcium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
| Replicates
A
Samp.
#
Used
xx
B
Sample
Wt.
(g)
XX. X
c
Solution
Vol.
(mL)
XX. X
E5
D
Result
(PH)
x.xx
===========
E
SD
XXX . XX
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(PH)
x.xx
Figure B-52. Form QC-18, quality control pH In 0.002 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 59 of 103
Form # QC-19
Submission #
Run # _
Re-Analysis
Parameter - CA_CL2
Calcium in Calcium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
A
Samp.
ff
Used
XX
B | C
1
Sample | Initial
Wt. | Soln.
| Vol.
(g) | (mL)
XX . XX | XX . X
1
1
1
D
1
Aliquot
Vol.
(mL)
XX. XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
F I
Inst. |
Reading j
1
(mg/L) |
XXX. XX |
1
1
1
G
— __
Calculated
Result
(meq/lOOg)
xxx . xxx
H
SD
or
% RSD
xxx. xx
Matrix Spikes
A | B
i ________
— — 1 — _
Samp. | Sample
# I Allq.
Used I Vol.
1 (mL)
XX | XX . XX
c
Vol.
Spike
Added
(mL)
XX . XXX
D
____ _____
Cone.
Spike
Added
(mg/L)
XXXX . X
E
Aliq.
Vol.
(mL)
XX. XX
F
Tot.
Diluted
Vol.
(mL)
xxx . xx
===== ===,==£=
G
Inst.
Reading
(mg/L)
XXX . XX
— — ;— — =
H
Spike
Recovery
(%)
XXX. XX
:==:=:=:=:======_===:==:=
=========
QCCS
True
High
Low
QCCS
QCCS
QCCS
I (mg/L)
| XXX.XX
QCCS 4 |
QCCS 5 |
QCCS 6 I
QCCS 7 j
QCCS 8 I
| DL-QCCS (mg/L)
j xxx . xx
| ==================
True
High
Low
Meas.
==================
Calib.
Blank
_===:__=:=_=_==
CBLKl
CBLK2
CBLK3
CBLK4
CBLK5
CBLK6
CBLK7
CBLK8
=========
(mg/L)
xxx. xx
===========
===========
Spike
Solution
==========
Inst.
Reading
(mg/L)
XXX . XX
==========
==========
==========
==========
Figure B-53. Form QC-19, quality control calcium In 0.002 M calcium chloride.
-------
Append ixB
Revision 0
Date: 8/90
Page 60 of 103
Form # QC-20
Submission #
Run # —
Re-Analysis
Parameter - MG_CL2
Magnesium in Calcium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replic
A
Samp.
Used
XX
;ates
B
Sample
Wt.
(g)
XX. XX
c
Initial
Soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. XX
==:==========
E
Total
Diluted
Vol.
(mL)
XXX. XX
F
Inst.
Reading
(mg/L)
XXX. XX
==
G
Calculated
Result
(meq/lOOg)
XXX. XXX
n=
H
SD
or
% RSD
xxx. xx
Matrix Spikes
A | B
Sample
# I Aliq.
Used | Vol.
I (mL)
XX | XX . XX
~~~~1~~~~~
J_
7
£==:=:=SS=:===
c
Vol.
Spike
Added
(mL)
XX . XXX
~~'~~~
D
Cone.
Spike
Added
(mg/L)
XXXX . X
E
Aliq.
Vol.
(mL)
XX. XX
F
Tot.
Diluted
Vol.
(mL)
XXX. XX
G
Inst.
Reading
(mg/L)
XXX . XX
\_
H
Spike
Recovery
(%)
XXX. XX
J_
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg/L)
XXX . XX
DL-QCCS
True
High
Low
Meas.
(mg/L)
xxx . xx
Calib.
Blank
CBLK1
CBLK2
CBLK3
CBLK4
CBLK5
CBLK6
CBLK7
CBLK8
(mg/L)
XXX. XX
Figure B-54. Form OC-20, quality control magnesium In 0.002 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 61 of 103
Form # QC-21
Submission #
Run |
Re-Analysis ~~
Parameter - K_CL2
Potassium in Calcium Chloride
Batch I
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Repli<
A
Samp.
#
Used
XX
=:======
:ates
B
Sample
Wt.
(g)
XX. XX
C | D | E
Initial | Aliquot | Total
Soln. | Vol. | Diluted
Vol. | | Vol.
(mL) | (mL) | (mL)
XX. X | XX. XX I XXX. XX
1 1
£ \_
_ _
F
Inst.
Reading
(mg/L)
XXX. XX
1 G
| Calculated
| Result
1
| (meq/lOOg)
1 XXX. XXX
1 1
1 _ 1
1
H
SD
or
% RSD
XXX. XX
1
Matrij
A
Samp.
#
Used
XX
< Spikes
B
Sample
Aliq.
Vol.
(mL)
XX. XX
C
Vol.
Spike
Added
(mL)
XX . XXX
— •^-——•s- -——-——-
====a= ======
D
Cone.
Spike
Added
(mg/L)
xxxx . x
E
Aliq.
Vol.
(mL)
XX. XX
==3=:========
=====3===::===
F
Tot.
Diluted
Vol.
(mL)
XXX. XX
=====:=:=:===s=
===:====5S==:=:3
G
Inst.
Reading
(mg/L)
XXX . XX
s==s=:=s=s======
ss
==
=s
H
Spike
Recovery
(%)
XXX. XX
=====S3===K===
=====s======
===:==£== =====
QCCS
True
High
LOW
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
(mg/L)
XXX.XX
DL-QCCS
True
High
Low
Meas.
(mg/L)
xxx.xx
Calib.
Blank
CBLK1
CBLK2
CBLK3
CBLK4
CBLK5
CBLK6
CBLK7
CBLK8
======£==
(mg/L)
xxx.xx
QCCS 8
Figure B-55. Form QC-21, quality control potassium In 0.002 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 62 of 103
Form # QC-22
Submission #
Run # ~
Re-Analysis
Replicates
ABC
Samp. Sample Initia
# Wt. Soln.
Used Vol .
(g) (mL)
XX XX . XX XX . Ji
_
1 1
Parameter - NA CL2
Sodium in Calcium Chi or J
| D | E
1 Aliquot | Total
Vol. | Diluted
j Vol.
(mL) | (mL)
XX. XX I XXX. XX
1 1
1 1
1 1
Batch ft
ide Lab Code
Date Analysis Started / /
Date Analysis Completed / /
Date Form Completed / /
Lab Manager Initials
F G H
—
Inst. Calculated SD
Reading Result or
j % RSD
(mg/L) | (meq/lOOg)
XXX. XX j XXX. XXX XXX. XX
__= \_ = I
1
II II
Matrix
A
Samp.
#
Used
XX
c Spikes
B
Sample
Allq.
Vol.
(mL)
XX. XX
c
Vol.
Spike
Added
(mL)
XX . XXX
D
Cone.
Spike
Added
(mg/L)
xxxx.x
E
Aliq.
Vol.
(mL)
XX. XX
F
Tot.
Diluted
Vol.
(mL)
XXX . XX
G
Inst.
Reading
(mg/L)
XXX . XX
H
Spike
Recovery
(%)
xxx. xx
QCCS
==========
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
=S===s===s=:=
(mg/L)
XXX . XX
=========
DL-QCCS | (mg/L)
XXX.XX
True
High
Low
Meas.
Calib.
Blank
CBLK1
CBLK2
CBLK3
CBLK4
CBLK5
CBLK6
CBLK7
CBLK8
(mg/L)
XXX.XX
Figure B-56. Form QC-22, quality control sodium In 0.002 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 63 of 103
Form # QC-23
Submission #
Run I
Re-Analysis
Parameter - FE CL2
Iron in Calcium Cfiloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
I A
Samp.
#
Used
XX
B
Sample
Wt.
(g)
XX. XX
C | D | E
Initial | Aliquot | Total
Soln. | Vol. | Diluted
Vol. | | Vol.
(mL) | (mL) | (mL)
XX . X | XX . XX | XXX . XX
I I
I I
I I
F
Inst.
Reading
(mg/L)
XXX. XX
I G
| Calculated
| Result
I
| (meq/lOOg)
| XXX . XXX
I
I
I
H
SD
or
% RSD
XXX . XX
Matrix Spikes
A | B
Sample
# | Aliq.
Used | Vol.
I (mL)
XX | XX . XX
_°"_~r~""~
i
c
Vol.
Spike
Added
(mL)
XX . XXX
D
Cone.
Spike
Added
(mg/L)
xxxx . x
E
Aliq.
Vol.
(mL)
XX. XX
_-
"
F
Tot.
Diluted
Vol.
(mL)
XXX . XX
G
Inst.
Reading
(mg/L)
XXX . XX
H
Spike
Recovery
(%)
XXX . XX
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg/L)
XXX . XX
~~
===:=======
| DL-QCCS
1
| =
| True
| High
| Low
j Meas .
==========
(mg/L)
XXX . XX
=========
==:===:
=a===:s===
Calib.
Blank
CBLK1
CBLK2
CBLK3
CBLK4
CBLK5
CBLK6
CBLK7
CBLK8
=========
=:========.
(mg/L)
XXX. XX
==========
Figure B-57. Form QC-23, quality control Iron In 0.002 M calcium chloride.
-------
Appendix B
Revision 0
Date: 8/90
Page 64 of 103
Form | QC-24
Submission #
Run #
Re-Analysis
Parameter - AL_CL2
Aluminum in Calcium Chloride
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
A
Samp.
Used
XX
B
Sample
Wt.
(g)
XX. XX
C | D | E
Initial | Aliquot | Total
Soln. j Vol. j Diluted
Vol. j j Vol.
(mL) j (mL) j (mL)
XX. X j XX. XX I XXX. XX
F
Inst.
Reading
(mg/L)
XXX. XX
I I I
I I I I
I I I
G
Calculated
Result
(meq/lOOg)
XXX. XXX
I
I
I
H
SD
or
% RSD
XXX. XX
I
I
Matri:
A
Samp.
#
Used
XX
< Spikes
B | C
|
Sample | Vol.
Aliq. | Spike
Vol . j Added
(mL) | (mL)
XX. XX | XX. XXX
I
I
I
_ _
D
Cone.
Spike
Added
(mg/L)
xxxx.x
E | F | G
Aliq. | Tot. | Inst.
Vol. | Diluted | Reading
I Vol . |
(mL) | (mL) | (mg/L)
XX. XX I XXX. XX I XXX. XX
I I
I I
I I
==
H
Spike
Recovery
(%)
XXX . XX
QCCS
True
High
Low
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
1
2
3
4
5
6
7
8
(mg/L)
XXX. XX
=========
DL-QCCS
True
High
Low
Meas.
(mg/L) |
XXX.XX I
Calib.
Blank
=========
CBLK1
CBLK2
CBLK3
CBLK4
CBLK5
CBLK6
CBLK7
CBLK8
zsssstsssssssssss
(mg/L) |
XXX . XX
===========
Figure B-58. Form QC-24, quality control aluminum In 0.002 M calcium chloride.
-------
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-------
Appendix B
Revision 0
Date: 8/90
Page 66 of 103
Form | QC-17
Submission #
Run #
Re-Analysis
Parameter - AC BACL
Barium Chloride-TEA" Acidity
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
A
—
Samp.
#
Used
XX
B
Sample
Wt.
(g)
x.xx
C | D
1
Titrant | Acid
Vol. | Normality
1
(mL) | N
XXX. XX | X.XXXX
1
1
1
E
Calculated
Result
(meq/lOOg)
XXX . XXX
F
SD
or
% RSD
XXX . XX
1
II
II
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mL)
XXX.XX
DL-QCCS
True
High
Low
Meas.
(mL)
XXX.XX
Calib.
Blank
CBLK1
CBLK2
CBLK3
CBLK4
CBLK5
CBLK6
CBLK7
CBLK8
(mL)
XXX. XX
Figure B-60. Form QC-17, quality control barium chlorlde-TEA acidity.
-------
Appendix B
Revision 0
Date: 8/90
Page 67 of 103
Form # 25
Submission #
Run #
Re-Analysis
Parameter - FE_PYP
Pyrophosphate Extraetable Iron
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
|
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK2
RBLK3
B
Sample
Wt.
(g)
x.xx
xxxxxxxx
xxxxxxxx
xxxxxxxx
c
Initial
Soln.
Vol.
(mL)
XXX. X
D
Aliquot
Vol.
(mL)
XXX . XX
E
Total
Diluted
Vol.
(mL)
xxx . xx
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(wt. %)
XX . XXX
XXXXXXXXXXXX
XXXXXXXXXXXX
xxxxxxxxxxxx
Figure B-61. Form 25, pyrophosphate extractable Iron.
-------
Appendix B
Revision 0
Date: 8/90
Page 68 of 103
Form #26
Parameter - AL_PYP
Pyrophosphate Extractable Aluminum
Batch #
Lab Code
Submission #
Run #
Re-Analysis
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
I A
I Samp.
*
I
2
3
I 4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK2
RBLK3
B
___ _
Sample
Wt.
(g)
x.xx
XXXXXXXX
xxxxxxxx
XXXXXXXX
c
Initial
Soln.
Vol.
(mL)
XXX. X
D
Aliquot
Vol.
(mL)
XXX. XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
F
Inst.
Reading
(mg/L)
XXX. XX
G
Calculated
Result
(wt. %)
XX. XXX
XXXXXXXXXXXX
XXXXXXXXXXXX i
xxxxxxxxxxxx
Figure B-62. Form 26, pyrophosphate extractable aluminum.
-------
Appendix B
Revision 0
Date: 8/90
Page 69 of 103
Form # 27
Submission #
Run | ~
Re-Analysis
Parameter - FE AO
Acid Oxalate Extractable Iron
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK2
RBLK3
B
Sample
Wt.
(g)
x.xx
xxxxxxxx
xxxxxxxx
xxxxxxxx
c
Initial
Soln.
Vol.
(mL)
XXX. X
D
Aliquot
Vol.
(mL)
XXX . XX
E
Total
Diluted
Vol.
(mL)
xxx . xx
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
1 (wt. %)
xx . xxx
1
1
1
1
1
I
I
XXXXXXXXXXXX
xxxxxxxxxxxx
xxxxxxxxxxxx
Figure B-63. Form 27, acid oxalate extractable Iron.
-------
Appendix B
Revision 0
Date: 8/90
Page 70 of 103
Form # 28
Submission #
Run f
Re-Analysis
Parameter - AL AO
Acid Oxalate ExtractaBle Aluminum
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
B
Sample
Wt.
(g)
x.xx
XXXXXXXX
RBLK2 | XXXXXXXX
RBLK3 | XXXXXXXX
C D E
Initial | Aliquot Total
Soln. Vol. Diluted
Vol . Vol .
(mL) (mL) (mL)
XXX. X XXX. XX XXX. XX
I
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(wt. %)
XX. XXX
1
XXXXXXXXXXXX
XXXXXXXXXXXX
XXXXXXXXXXXX
Figure B-64. Form 28, acid oxalate extractable aluminum.
-------
Appendix B
Revision 0
Date: 8/90
Page 71 of 103
Form # 29
Parameter - SI AO
Acid Oxalate ExtractaBle Silicon
Batch #
Lab Code
Submission #
Run #
Re-Analysis
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A B
Samp. Sample
# Wt.
(g)
i
2
3
4
5
x.xx
6
7
8
9
10
11
12
13
14
15
16
17
18
19
| 20
21
22
23
24
25
26
27
c
Initial
Soln.
Vol.
(mL)
XXX. X
D E
Aliquot Total
Vol. Diluted
Vol.
(mL) (mL)
XXX . XX XXX . XX j
1
i
1
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK2
RBLK3 |
1
XXXXXXXX
xxxxxxxx
XXXXXXXX
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(wt. %)
XX. XXX
1
| XXXXXXXXXXXX |
j XXXXXXXXXXXX
XXXXXXXXXXXX
— ^ — T— i_iiEg— — .— -^^— i—
Figure B-65. Form 29, acid oxalate extractable silicon.
-------
Appendix B
Revision 0
Date: 8/90
Page 72 of 103
Form # 30
Submission #
Run #
Parameter - FE_CD
Citrate Dithionite Extractable Iron
Batch #
Lab Code
Re-Analysis
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
ABC D
Samp. Sample Initial Aliquot
# Wt. Soln. vol.
Vol.
(g)
x.xx
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK2
(mL)
XXX. X
1
E F
Total Inst.
Diluted Reading
Vol.
(mL) (mL)
XXX . XX XXX . XX
(mg/L)
XXXXXXXX
XXXXXXXX
RBLK3 | XXXXXXXX
XXX . XX
G
Calculated
Result
(wt. %)
1
XX. XXX
1
i
1
1
1
XXXXXXXXXXXX
xxxxxxxxxxxx
XXXXXXXXXXXX
Figure B-66. Form 30, citrate dithlonlte extractable Iron.
-------
Appendix B
Revision 0
Date: 8/90
Page 73 of 103
Form # 31
Submission #
Run #
Parameter - AL_CD
Citrate Dithionite Extractable Aluminum
Batch #
Lab Code
Re-Analysis
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
ABC
| Samp .
w
Sample Initial
Wt. Soln.
Vol.
(g) (mL)
D
Aliquot
Vol.
E
Total
Diluted
Vol.
(mL) (mL)
F | G
Inst. | Calculated
Reading | Result
I
(mg/L)
X.XX XXX. X XXX. XX XXX. XX XXX. XX
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
— _ —
I
1 (wt. %)
| XX . XXX
i
i
27
28
29
30
31
32
33
34
35
36
37
38
1
1
1
i
39
40
41
42
RBLK1 | XXXXXXXX
RBLK2 | XXXXXXXX
RBLK3 j XXXXXXXX
I
| XXXXXXXXXXXX
1 XXXXXXXXXXXX 1
XXXXXXXXXXXX 1
Figure B-67. Form 31, citrate dithlonlte extractable aluminum.
-------
Appendix B
Revision 0
Date: 8/90
Page 74 of 103
Form # QC-25
Submission #
Run #
Re-Analysis
Replicates
Parameter - FE PYP
Pyrophosphate Extractable Iron
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
i
Used
XX
=======
=======
B
Sample
Wt.
(g)
x.xx
==========
=====::=====
c
Init.
Soln.
Vol.
(mL)
XXX. X
==========
==========
D
Aliq.
Vol.
(mL)
XXX . XX
==========
E
Total
Diluted
Vol.
(mL)
XXX. XX
===========
======:===:==
==
==
F
Inst.
Reading
(mg/L)
XXX. XX
===========
====:====:===
1 G
| Calculated
| Result
1
1 (wt. %)
| XX. XXX
===============
1
1
1
H
SD
or
% RSD
XXX . XX
=========
=========
Matrix J
A
Samp.
Used
XX
_.
QCCS
True
High
Low
QCCS 1
QCCS 3
QCCS 4
QCCS 5
QCCS 7
QCCS 8
=========5=
Spikes
B I
Sample |
Aliq. |
Vol. |
(mL) |
XXX . XX j
]__
1
1
(mg/L)
XXX . XX
============================================================
C D E F | G | H
Vol. Cone. Aliq. Total | Inst. | Spike
Spike Spike Vol. Diluted Reading | Recovery
Added Added Vol. |
(mL) (mg/L) (mL) (mL) | (mg/L) | (%)
XX . XXX XXXX . X XXX . XX XXX . XX 1 XXX . XX I XXX . XX
II 1
1 1 1
f II 1
| DL-QCCS (mg/L) Calib. | (mg/L)
j xxx. xx Blank j xxx.xx
True CBLKl |
High CBLK2
Low CBLK3
Meas . CBLK4
CBLK6
CBLK7
CBLK8 |
Figure B-68. Form QC-25, quality control pyrophosphate extractable Iron.
-------
Appendix B
Revision 0
Date: 8/90
Page 75 of 103
Form # QC-26
Submission #
Run #
Re-Analysis
Parameter - AL PYP
Pyrophosphate ExtractaBle Aluminum
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
A | B | C
Samp.
Used
XX
=
1
Sample j Init.
Wt. j Soln.
| Vol.
(g) | (mL)
X . XX | XXX . X
1
D
Aliq.
Vol.
(mL)
XXX . XX
I~HZ_L I 1
-__ ^
E |
1
Total |
Diluted
Vol.
(mL)
XXX. XX
1
\_
_
1 F
1 _
Inst.
Reading
(mg/L)
xxx . xx
1
G
Calculated
Result
(wt. %)
XX. XXX
J_
J_ J__
_
"
1 H
| SD
1 or
j % RSD
|
j XXX. XX
J_
1
1
Matrix i
A I
Samp . |
# 1
Used |
j
XX |
:s:5s===2====
1
1
1
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
Spikes
B
Sample
Aliq.
Vol.
(mL)
XXX . XX
==========
1
1
(mg/L)
XXX . XX
C | D | E
Vol. | Cone. | Aliq.
Spike | Spike | Vol.
Added | Added |
(mL) | (mg/L) | (mL)
XX. XXX | XXXX.X | XXX. XX
=================:============
1 1
1 1
\_ J^
DL-QCCS (mg/L)
XXX. XX
True
High
Low
Meas.
==================
F G | H
Total Inst. Spike
Diluted Reading Recovery
Vol.
(mL) (mg/L) (%)
XXX. XX XXX. XX j XXX. XX
:3=========:==========:============
1 11
1 II
\_ 1 I
Calib. (mg/L)
Blank xxx. xx
CBLK1
CBLK2
CBLK3
CBLK4
CBLK5
CBLK6
CBLK7
CBLK8
=================
Figure B-69. Form QC-26, quality control pyrophosphate extractable aluminum.
-------
Appendix B
Revision 0
Date: 8/90
Page 76 of 103
Form # QC-27
Submission #
Run |
Re-Analysis
Parameter - FE_AO
Acid Oxalate Extractable Iron
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replic
A
Samp.
#
Used
XX
:ates
B
Sample
Wt.
(g)
x.xx
c
Init.
Soln.
Vol.
(mL)
XXX. X
D
Aliq.
Vol.
(mL)
XXX . XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
F
Inst.
Reading
I
I (n>g/L)
| XXX . XX
I
I
G
Calculated
Result
(wt. %) |
xx . xxx |
I
I
H
SD
or
% RSD
XXX . XX
II
Matrix
A I
Samp . |
Used
XX
I
I
I I
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
Spikes
B
Sample
Aliq.
Vol.
(mL)
XXX . XX
1
1
1
(mg/L)
| XXX . XX
C D | E F
Vol. Cone. | Aliq. Total
Spike Spike | Vol. Diluted
Added Added | Vol.
(mL) (mg/L) | (mL) (mL)
XX. XXX XXXX.X I XXX. XX XXX. XX
1 1 1
1 1 1
1 1 1
DL-QCCS | (mg/L) Calib.
| xxx. xx Blank
True | CBLK1
High | CBLK2
Low j CBLK3
Meas . | CBLK4
================== CBLK5
CBLK6
CBLK7
CBLK8
1
6 H
Inst. Spike
Reading Recovery
(mg/L) (%)
XXX. XX | | XXX. XX
II
— =======
II
(mg/L)
XXX. XX
Figure B-70. Form QC-27, quality control acid oxalate extractable Iron.
-------
Appendix B
Revision 0
Date: 8/90
Page 77 of 103
Form # QC-28
Submission I
Run #
Re-Analysis
Parameter - AL AO
Acid Oxalate ExtractabTe Aluminum
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
A
Samp.
#
Used
XX
=
B
Sample
Wt.
(g)
x.xx
1
Matrix Spikes
A | B
Samp.
Used
XX
==;===:==
1
1 Sample
| Aliq.
| Vol.
| XXX. XX
1
1
~l
c
Init.
Soln.
Vol.
(mL)
XXX. X
_
C
Vol.
Spike
Added
XX . XXX
D
Aliq.
Vol.
(mL)
XXX . XX
1
_"_I~ - I
1
| Cone .
j Spike
| Added
1 (mg/L)
| XXXX . X
1
1
1
E
Total
Diluted
Vol.
(mL)
XXX . XX
1
E
Aliq.
Vol.
(mL)
XXX . XX
==========
F |
Inst. |
Reading |
(mg/L) |
XXX . XX |
1 1
!_ \_
1 !
F |
Total |
Diluted |
Vol. |
(mL) |
XXX . XX |
1
G H
Calculated SD
Result or
| % RSD
(wt. %) |
XX . XXX 1 XXX . XX
1
1
1
G H
Inst. Spike
Reading Recovery
(mg/L) (%)
XXX . XX XXX . XX
-^
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg/L)
XXX.XX
DL-QCCS
True
High
Low
Meas.
(mg/L)
XXX.XX
Calib.
Blank
CBLK1
CBLK2
CBLK3
CBLK4
CBLK5
CBLK6
CBLK7
CBLK8
(mg/L)
XXX.XX
Figure B-71. Form QC-28, quality control acid oxalate extractable aluminum.
-------
Appendix B
Revision 0
Date: 8/90
Page 78 of 103
Form # QC-29
Submission i
Run # ~
Re-Analysis
Parameter - SI AO
Acid Oxalate Extractable Silicon
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Repli(
A
Samp.
Used
XX
=======
;ates
B
Sample
Wt.
(g)
x.xx
======;==:=::
:= =====:===::
C
Init.
Soln.
Vol.
(mL)
XXX. X
===:===s====
===:=== ==s::
D
Aliq.
Vol.
(mL)
XXX. XX
==========
E
Total
Diluted
Vol.
(mL)
XXX . XX
===========
==
==
F
Inst.
Reading
(mg/L)
XXX. XX
S3
=r
G
Calculated
Result
(wt. %)
kx . xxx
H
SD
or
% RSD
XXX . XX
Matrix Spikes
A
Samp.
f
Used
XX
B
—
Sample
Aliq.
Vol.
(mL)
XXX . XX
I
I
I
C
Vol.
Spike
Added
(mL)
XX . XXX
D | E
1
Cone. | Alig.
Spike | Vol.
Added |
(mg/L) | (mL)
XXXX.X | XXX. XX
I I
I I
I I
F
Total
Diluted
Vol.
(mL)
XXX. XX
I G |
1
| Inst. j
| Reading |
I |
I (mg/L) |
I xxx. xx |
II I
1 1 I
II I
H
Spike
Recovery
(%)
xxx . xx
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg/L)
XXX . XX
1
DL-QCCS
========s==
True
High
Low
Meas.
(mg/L)
XXX. XX
Calib.
Blank
CBLK1
CBLK2
CBLK3
CBLK4
CBLK6
CBLK7
CBLK8
(mg/L)
XXX . XX
Figure B-72. Form QC-29, quality control acid oxalate extractable silicon.
-------
Appendix B
Revision 0
Date: 8/90
Page 79 of 103
Form # QC-30
Submission #
Run I
Re-Analysis
Parameter - FE_CD
Citrate 'Dithionite Extractable Iron
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Repli(
A
Samp.
Used
XX
:ates
B
Sample
Wt.
(g)
x.xx
c
Init.
Soln.
Vol.
(mL)
XXX. X
D
Aliq.
Vol.
(mL)
XXX . XX
E |
Total |
Diluted |
Vol. |
(mL) |
XXX . XX |
I
I
I
F
Inst.
Reading
(mg/L)
XXX . XX
G
Calculated
Result
(wt. %)
xx . xxx
H
SD
or
% RSD
XXX . XX
Matrix Spikes
A B
1
Samp. Sample Vol.
# Aliq. | Spike
Used Vol. j Added
(mL) I (mL)
XX j XXX.XX I XX.XXX
E
I
Cone. | Aliq. | Total
Spike j Vol. | Diluted
Added j | Vol.
(mg/L) | (mL) | (mL)
xxxx.x I xxx.xx I xxx.xx
I
Inst.
Reading
(mg/L)
XXX.XX
Spike
Recovery
XXX. XX
.11
77
QCCS
=========
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg/L) |
XXX . XX
=========
| DL-QCCS
1
1
| True
| High
| Low
| Meas.
(mg/L) |
XXX . XX |
1
1
Calib.
Blank
CBLK1
CBLK2
CBLK3
CBLK4
CBLK5
CBLK6
CBLK7
CBLK8
(mg/L)
XXX . XX
Figure B-73. Form QC-30, quality control citrate dithlonlte extractable Iron.
-------
Appendix B
Revision 0
Date: 8/90
Page 80 of 103
Form # QC-31
Parameter - AL_CD
Citrate Dithionite Extractable Aluminum
Batch #
Lab Code
Submission #
Run #
Re-Analysis
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Repli<
=1=====:
A
Samp.
#
Used
XX
:ates
B | C
Sample | Init.
Wt. | Soln.
| Vol.
(g) | (mL)
X . XX | XXX . X
1 1
—?——.——-—— — — — —-_———-———__ ——__-—_
1 '
1 1
D
Aliq.
Vol.
(mL)
XXX. XX
===========
Total
Diluted
Vol.
(mL)
XXX . XX
F |
Inst.
Reading
(mg/L) |
XXX. XX |
1
G
Calculated
Result
(wt. %)
XX . XXX
II II 1
H
SD
or
% RSD
XXX. XX
1 II II
Matrix Spikes
A | B
1
Samp. | Sample
# | Aliq.
Used j Vol .
1 (mL)
XX | XXX. XX
C
Vol.
Spike
Added
(mL)
XX . XXX
D
Cone.
Spike
Added
(mg/L)
XXXX . X
E | F
Aliq. | Total
Vol. | Diluted
| Vol.
(mL) | (mL)
XXX . XX | XXX . XX
G
Inst.
Reading
(mg/L)
XXX . XX
H
Spike
Recovery
(%)
XXX . XX
11
==.====.==:;:
| QCCS
1
True
High
Low
QCCS 1
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
=======s==s
(mg/L)
XXX . XX
DL-QCCS
True
High
Low
Meas.
(mg/L)
XXX. XX
=========
Calib.
Blank
CBLK1
CBLK2
CBLK3
CBLK4
CBLK6
CBLK7
CBLK8
======:=:==
(mg/L)
XXX . XX
=========
Figure B-74. Form QC-31, quality control citrate dithlonlte extractable aluminum.
-------
Appendix B
Revision 0
Date: 8/90
Page 81 of 103
Form # 32
Submission #
Run #
Re-Analysis
Parameter - SO4_H20
Water Extractable Sulfate
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK2
RBLK3
B
Sample
Wt.
(g)
x.xx
XXXXXXXX
xxxxxxxx
XXXXXXXX
c
Initial
Soln.
Vol.
(mL)
XXX. X
D
Aliquot
Vol.
(mL)
XXX . XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
F
w « _*
Inst.
Reading
~XV
(mg S/L)
XXX . XX
G
Calculated
Result
(mg S/kg)
XXX . XXX
XXXXXXXXXXXX
xxxxxxxxxxxx
XXXXXXXXXXXX
Figure B-75. Form 32, water extractable sulfate.
-------
Appendix B
Revision 0
Date: 8/90
Page 82 of 103
Form # 33
Submission #
Run #
Re-Analysis
Parameter - SO4_PO4
Phosphate Extractable Sulfate
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK2
RBLK3
B
Sample
Wt.
(g)
x.xx
XXXXXXXX
xxxxxxxx
XXXXXXXX
c
__« ___«
* Final
Soln.
Vol.
(mL)
XXX. X
D
Aliquot
Vol.
(mL)
XXX . XX
E
___ _«^_
Total
Diluted
Vol.
(mL)
XXX . XX
F
Inst.
Reading
(mg S/L)
XXX . XX
G
Calculated
Result
(mg S/kg)
XXX . XXX
1
XXXXXXXXXXXX |
xxxxxxxxxxxx i
xxxxxxxxxxxx i
Figure B-76. Form 33, phosphate extractable sulfate.
-------
Appendix B
Revision 0
Date: 8/90
Page 83 of 103
Form # QC-32
Submission #
Run #
Re-Analysis
Parameter - S04_H20
Water Extractable Sulfate
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
A
Samp.
#
Used
XX
B | C
Samp. j Initial
Wt. | Soln.
| Vol.
(5) I (mL)
x.xx I xxx. x
~ ___!_ _
i
D
Aliq.
Vol.
(mL)
xxx. xx
E |
— ~ — — — I
Total |
Diluted |
Vol. |
(mL) |
xxx. xx )
I~__~_~_l
I
F
Inst.
Reading
(mg S/L)
XXX . XX
G
Calculated
Results
(mg S/kg)
xxx . xxx
H
SD
or
% RSD
XXX . XX
11
11
Matrix Spikes
A
Samp.
*
Used
XX
B
Sample
Aliq.
Vol.
(mL)
xxx . xx
I I
C | D
Vol. | Cone.
Spike | Spike
Added | Added
(mL) | (mg/L)
XX . XXX | XXXX . X
I
I
I
E
Aliq.
Vol.
(mL)
XXX. XX
F |
Total |
Diluted |
Vol. |
(mL) |
xxx. xx I
I
I
I
f*
Inst.
Reading
(mg S/L)
xxx . xx
H
Spike
Recovery
(%)
XXX. XX
I
I
QCCS
True
High
Low
QCCS
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
1 I
I
(mg S/L)
XXX.XX
I QCCS 8 I
DL-QCCS
True
High
Low
Meas.
(mg S/L)
xxx . xx
Calib.
Blank
CBLKl
CBLK2
CBLK3
CBLK4
CBLK5
CBLK6
CBLK7
CBLK8
(mg S/L)
XXX . XX
Figure B-77. Form QC-32, quality control water extractable sulfate.
-------
Appendix B
Revision 0
Date: 8/90
Page 84 of 103
Form # QC-33
Submission f
Run #
Re-Analysis
Parameter - S04_PO4
Phosphate Extractable Sulfate
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
A B
Samp . Samp .
# Wt.
Used
(g)
XX X . XX
c
Initial
Soln.
Vol.
(mL)
XXX. X
D
Aliq.
Vol.
(mL)
XXX. XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
F
Inst.
Reading
(rag S/L)
XXX. XX
G
Calculated
Results
(mg S/kg)
XXX . XXX
==
::====:= ==s s:
H
SD
or
% RSD
xxx. xx
II
Matrij
A
_
Samp.
#
Used
XX
c Spikes
B
Sample
Alrq.
Vol.
(mL)
XXX . XX
c
Vol.
Spike
Added
(mL)
XX . XXX
1
1
V
Cone.
Spike
Added
(mg/L)
xxxx . x
E
— — — — — — — —
Aliq.
Vol.
(mL)
XXX . XX
F
— — — — —
Total
Diluted
Vol.
(mL)
XXX . XX
KS
G
Inst.
Reading
(mg S/L)
XXX . XX
1
1
1
_ _
j Spike
j Recovery
1 (%)
| XXX. XX
1
1
1
QCCS
True
High
Low
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
1
2
3
4
5
6
7
8
(mg S/L)
XXX. XX
I DL-QCCS |
True
High
Low
Meas.
(mg S/L)
XXX.XX
Calib.
Blank
CBLK1
CBLK2
CBLK3
CBLK4
CBLK5
CBLK6
CBLK7
CBLK8
(mg S/L)
XXX.XX
Figure B-78. Form QC-33, quality control phosphate extractable sulfate.
-------
Appendix B
Revision 0
Date: 8/90
Page 85 of 103
DIRECT/DELAYED RESPONSE PROJECT (DDRP) SOIL SURVEY
FORM 113
QUALITY CONTROL: ION CHROMATOGRAPHY RESOLUTION TEST
LAB NAME
BATCH ID
UAH. UP ANALYSIS
LAB MANAGER'S SIGNATURE
1C Make and Model:
rWDD/YR
Concentration
(mg/L)
Peak Area
(Integrator units)
so|-
Peak Height
(cm)
NO,
Column Back Pressure (at max. of stroke):
Flow Rate: _____________
Column Model:
Date of Purchase:
Column Manufacturer:
Column Serial Ho:
Precolumn in system
Yes
No
*1UO x 2(tr2-tri)/(Hi+W2) N03 - P04
Percentage Resolution: 100 x ZU^-trzi/lw.+Hj) P0
-------
Appendix B
Revision 0
Date: 8/90
Page 86 of 103
Form # 34
Submission f
Run #
Re-Analysis
Parameter - S04_0
Zero mg S/L Isotherm Parameter
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
ABC
Samp. Sample Initial
# Wt. Soln.
| Vol.
I (g) (wL)
1
2
3
4
5
X . XX XX . X
D
Aliquot
Vol.
K | F
Total
Diluted
Vol.
(mL) (mL)
XX. XX
XXX . XX
6
7
8
9 |
10 |
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
i
41
42
RBLK1 | XXXXXXXX |
RBLK2 XXXXXXXX |
RBLK3 | XXXXXXXX |
Inst.
Reading
G
Calculated
Result
(mg S/L) (mg S/L)
XXX. XXX XXX. XXX
| XXXXXXXXXXXX
I XXXXXXXXXXXX
| XXXXXXXXXXXX
Figure B-80. Form 34, 0 mg S/L Isotherm.
-------
Appendix B
Revision 0
Date: 8/90
Page 87 of 103
Form # 35
Submission #
Run #
Re-Analysis
Parameter — S04 2
Two mg S/L Isotherm Frameter
Batch f
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
I A
I Samp .
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK2
RBLK3
B
Sample
Wt.
(g)
x.xx
| = as B
xxxxxxxx
xxxxxxxx
xxxxxxxx
c
Initial
Soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. XX
!
E
Total
Diluted
Vol.
(mL)
XXX . XX
F
Inst.
Reading
(mg S/L)
XXX . XXX
1
6
Calculated
Result
(mg S/L)
XXX . XXX
1
XXXXXXXXXXXX |
xxxxxxxxxxxx i
XXXXXXXXXXXX |
Figure B-81. Form 35, 2 mg S/L Isotherm.
-------
Append ixB
Revision 0
Date: 8/90
Page 88 of 103
'orra #36
Submission #
*un # ~
te-Analysis
Parameter - SO4_4
Four mg S/L Isotherm Panneter
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
f
1
B | C
Sample Initial
Wt. Soln.
(g)
x.xx
2 1
3
4 I
5 1
6
7
8
9
10
11
12
13
14 |
15 |
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. XX
1
E
Total
Diluted
Vol.
(mL)
XXX . XX
F
Inst.
Reading
(rag S/L)
XXX . XXX
1
30 |
31 |
32 |
33 |
34
35
36
37
38 |
39
40
41
42
RBLK1
RBLK2
XXXXXXXX
XXXXXXXX
RBLK3 | XXXXXXXX
G
Calculated
Result
(mg S/L)
XXX. XXX
XXXXXXXXXXXX 1
| XXXXXXXXXXXX |
XXXXXXXXXXXX |
Figure B-82. Form 36, 4 mg S/L Isotherm.
-------
Appendix B
Revision 0
Date: 8/90
Page 89 of 103
Form # 37
Submission #
Run #
Re-Analysis
Parameter - S04 8
Eight rag S/L Isotherm Parameter
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK2
RBLK3
B
Sample
Wt.
(g)
x.xx
xxxxxxxx
xxxxxxxx
xxxxxxxx
c
Initial
Soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
F
Inst.
Reading
(mg S/L)
XXX . XXX
G
Calculated
Result
(mg S/L)
XXX. XXX
1
xxxxxxxxxxxx
xxxxxxxxxxxx
xxxxxxxxxxxx
Figure B-83. Form 37, 8 mg S/L Isotherm.
-------
Appendix B
Revision 0
Date: 8/90
Page 90 of 103
Form # 38
Submission #
Run #
Re-Analysis
Parameter - S04_16
Sixteen mg S/L Isotherm Parameter
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A B
Samp. Sample
I Wt.
(g)
x.xx
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42 |
RBLK1 | XXXXXXXX
RBLK2 XXXXXXXX
RBLK3 XXXXXXXX
C D E | F
«H»~
Initial Aliquot Total
Soln. Vol. Diluted
Vol.
(KlL)
XX. X
(mL)
Vol.
Inst.
Reading
(mL) 1 (mg S/L)
XX. XX | XXX. XX
XXX . XXX
_
G
Calculated
Result
(mg S/L)
XXX . XXX
XXXXXXXXXXXX
XXXXXXXXXXXX
XXXXXXXXXXXX
Figure B-84. Form 38,16 mg S/L Isotherm.
-------
Appendix B
Revision 0
Date: 8/90
Page 91 of 103
Form # 39
Parameter - SO4_32
Thirty-two mg S/L Isotherm Parameter
Batch #
Lab Code
Submission #
Run f
Re-Analysis
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RBLK1
RBLK2
RBLK3
B
Sample
Wt.
(g)
x.xx
XXXXXXXX
xxxxxxxx
XXXXXXXX
c
Initial
Soln.
Vol.
(mL)
XX. X
D
Aliquot
Vol.
(mL)
XX. XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
F
Inst.
Reading
(mg S/L)
XXX . XXX
G
Calculated
Result
(mg S/L)
XXX . XXX
xxxxxxxxxxxx
XXXXXXXXXXXX j
xxxxxxxxxxxx
Figure B-85. Form 39, 32 mg S/L Isotherm.
-------
Appendix B
Revision 0
Date: 8/90
Page 92 of 103
Form f QC-34
submission #
Run f ~
Re-Analysis
Zero
Parameter - S04 0
mg S/L Isotherm Parameter
Batch #
Lab Code
Date Analysis started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replic
A
Samp.
Used
XX
:ates
B
Samp.
Wt.
(g)
x.xx
c
Initial
Soln.
Vol.
(mL)
XX. X
D
Aliq.
Vol.
(mL)
XX. XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
F
Inst.
Reading
(mg S/L)
XXX . XXX
G
Calculated
Results
(mg S/kg)
XXX . XXX
I
H I
SD
or
% RSD
XXX. XX
i QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
APPQ A.
VvV-O 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg S/L)
XXX . XXX
DL-QCCS
True
High
Low
Meas.
(mg S/L)
XXX . XXX
==========
Calib.
Blank
CBLK1
CBLK2
CBLK3
CBLK4
CBLK5
CBLK6
fRT V7
CtiljA/
CBLK8
=========
(mg S/L)
XXX . XXX
=SSS=;SSSSS£=3S
Spike
Solution
Inst.
Reading
(mg S/L)
XXX . XXX
==========
====S======
1
==========
Figure B-86. Form QC-34, quality control zero mg S/L Isotherm parameter.
-------
Appendix B
Revision 0
Date: 8/90
Page 93 of 103
Form # QC-35
Submission #
Run #
Re-Analysis
Parameter - SO4_2
Two mg S/L Isotherm Parameter
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replic
A
Samp.
f
Used
XX
;ates
B
Samp.
Wt.
(g)
x.xx
c
Initial
Soln.
Vol.
(mL)
XX. X
D
Aliq.
Vol.
(mL)
XX. XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
s:
=s
F
Inst.
Reading
(mg S/L)
XXX. XXX
£=
G
Calculated
Results
(mg S/kg)
XXX . XXX
H
SD
or
% RSD
XXX . XX
Matrix Spikes |
A
Samp.
#
Used
XX
=======
=======
1
B
Sample
Aliq.
Vol.
(mL)
XX. XX
C
Vol.
Spike
Added
(mL)
XX . XXX
D
Cone.
Spike
Added
(mg/L)
XXXX . X
============S====S======:S;=:SE===S:=
1
\_ 1
1 1
1 _l
E
Aliq.
Vol.
(mL)
XX. XX
F
Total
Diluted
Vol.
(mL)
XXX . XX
1
1
1
1
1
1
G
Inst.
Reading
(mg S/L)
XXX. XXX
===========
==:=========
H
Spike
Recovery
XXX . XX
===========
= —
===========
QCCS
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg S/L)
XXX. XXX
DL-QCCS
True
High
Low
Meas.
(mg S/L)
XXX.XXX
Spike
Solution
Inst.
Reading
(mg S/L)
XXX.XXX
Figure B-87. Form QC-35, quality control two mg S/L Isotherm parameter.
-------
Appendix B
Revision 0
Date: 8/90
Page 94 of 103
Form I QC-36
Submission #
Run #
Re-Analysis
Parameter - SO4_4
Four mg S/L Isotherm Parameter
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicates
A
Samp.
I
Used
XX
B
Samp.
Wt.
(g)
x.xx
c
Initial
Soln.
Vol.
(mL)
XX. X
D
Aliq.
Vol.
(mL)
XX. XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
==
F I
Inst.
Reading
(mg S/L)
XXX . XXX
G
Calculated
Results
(mg S/kg)
XXX . XXX
e=
sassas :=====
H
SD
or
% RSD
XXX . XX
| QCCS
! =
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(rog S/L)
XXX . XXX
1
1
1
DL-QCCS
True
High
Low
Meas.
(rag S/L)
xxx.xxx
Spike
Solution
S=S=^===5=S
Inst.
Reading
(mg S/L)
xxx.xxx
Figure B-88. Form QC-36, quality control four mg S/L Isotherm parameter.
-------
Append ixB
Revision 0
Date: 8/90
Page 95 of 103
Form # QC-37
Submission #
Run # ~
Re-Analysis
Parameter - SO4 8
Eight mg S/L Isotherm Parameter
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replic
A
Samp.
#
Used
XX
;ates
B | C
Samp. | Initial
Wt. | Soln.
| Vol.
(g) | (mL)
X . XX | XX . X
I
I
I
D
Aliq.
Vol.
(mL)
XX. XX
E
Total
Diluted
Vol.
(mL)
XXX . XX
F
Inst.
Reading
(mg S/L)
XXX . XXX
G
Calculated
Results
I
| (mg S/kg)
| xxx . xxx
I
I
I
H
SD
or
% RSD
XXX . XX
Matrix Spikes
A
Samp.
1
Used
XX
B
Sample
Alig.
Vol.
(mL)
XX. XX
c
Vol.
Spike
Added
(mL)
XX . XXX
1
1
D
Cone.
Spike
Added
(mg/L)
XXXX . X
E
Aliq.
Vol.
(mL)
XX. XX
F
Total
Diluted
Vol.
(mL)
XXX . XX
1
1
G
Inst.
Reading
(mg S/L)
xxx . xxx
1
H
Spike
Recovery
(%)
XXX . XX
I QCCS
True
High
j Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg S/L)
xxx . xxx
DL-QCCS
True
High
Low
Meas.
===:==s====
(mg S/L) |
xxx. xxx 1
1
1
1
1
Spike
Solution
Inst.
Reading
(mg S/L)
xxx . xxx
Figure B-89. Form QC-37, quality control eight mg S/L Isotherm parameter.
-------
Appendix B
Revision 0
Date: 8/90
Page 96 of 103
Form | QC-38
Submission #
Run #
Re-Analysis
Parameter - SO4_16
Sixteen mg S/L Isotherm Parameter
Batch #
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replic
A
_
Samp.
#
Used
XX
:ates
B
———————
Samp.
Wt.
(g)
x.xx
C | D
— —
Initial | Aliq.
Soln. | Vol.
Vol. |
(mL) | (mL)
XX . X | XX . XX
I
E
Total
Diluted
Vol.
(mL)
XXX . XX
F
Inst.
Reading
(mg S/L)
XXX. XXX
G I
— I
Calculated |
Results |
I
(mg S/kg) |
XXX . XXX |
I
H
SD
or |
% RSD
XXX . XX
QCCS
========-
True
High
Low
QCCS 1
QCCS 2
QCCS 3
QCCS 4
QCCS 5
QCCS 6
QCCS 7
QCCS 8
(mg S/L)
XXX . XXX
DL-QCCS
True
High
Low
Meas.
(mg S/L)
XXX.XXX
I spike |
j Solution |
Inst.
Reading
(mg S/L)
xxx.xxx
Figure B-90. Form QC-38, quality control sixteen mg S/L Isotherm parameter.
-------
Appendix B
Revision 0
Date: 8/90
Page 97 of 103
f QC-39
Parameter - SO4_32
Thirty-two mg S/L Isotherm Parameter
Batch #
Lab Code
Submission #
*un #
^e-Analysis
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replic
A
Samp.
Used
XX
;ates
B
Samp.
Wt.
-------
Appendix B
Revision 0
Date: 8/90
Page 98 of 103
Form #40
Batch #
Submission
Run f
Parameter - C_TOT
Total Carbon
Re-Analysis _
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
1
2
3
4
5
6
7
a
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
B
Sample
Wt.
(ug)
xxxxxx
C
Factor
(counts/
ug-wt%)
XX . XXX
D
Inst.
Reading
(counts)
xxxxxxxxxx
==E=3==S=E»S=3;
E
Blk. Inst
Reading
(counts)
xxxxx
===£=S=====£=S=
F
Calculated
Result
(wt %)
XX . XXX
Figure B-92. Form 40, total carbon.
-------
Appendix B
Revision 0
Date: 8/90
Page 99 of 103
Form # 41
Batch #
Submission #
Run #
Re-Analysis _
Parameter - N_TOT
Total Nitrogen
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
IT
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
B
Sample
Wt.
(ug)
xxxxxx
c
Factor
(counts/
ug-wt%)
XX. XXX
D
Inst.
Reading
(counts)
xxxxxxxxxx
E
Blk. Inst
Reading
(counts)
xxxxx
F
Calculated
Result
(wt %)
XX. XXX
====;====r:=
Figure B-93. Form 41, total nitrogen.
-------
Appendix B
Revision 0
Date: 8/90
Page 100 of 103
Form # QC-40
Batch #
Submission #
Run #
Re-Analysis _
I Replicate Data
Parameter - C_TOT
Total Carbon
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
#
====5
=====
B
Sample
Wt.
(ug)
xxxxxx
========
========
c
Factor
(counts/
ug-wt%)
XX. XXX
=======
========
D
Inst.
Reading
(counts)
xxxxxxxxxx
============
============
E
Blk. Inst
Reading
(counts)
xxxxx
=========
F
Calculated
Result
(wt %)
XX . XXX
==========
G
SD
or
%RSD
XXX . XX
==========
==========
| Matrix Spikes
A
Samp.
#
=====
=====
B
Sample
Wt.
(ug)
xxxxxx
=;=======
========
c
Cone.
Spike
Added
(wt %)
XX. XXX
======
=====
D
Spike
Added
(ug)
xxxxx
=====
=====
E
Factor
(count/
ug-wt%)
XX . XXX
=======
=======
F
Inst.
Reading
(counts)
xxxxxxxxxx
==========
==========
G
Blank
Inst.
Reading
(count)
xxxxx
=======
=======
H
Spike
plus
Sample
(wt %)
XX. XXX
========
========
I
Spike
Recovery
(%)
XXX. XX
========
========
QCCS
True
Low
High
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
1
2
3
4
5
6
7
8
(wt. %)
XX . XXX
DL-QCCS
True
Low
High
Meas.
(wt. %)
XX.XXX
Calib.
Blank
=======
CBLK
CBLK
CBLK
CBLK
CBLK
CBLK
CBLK
CBLK
===
1
2
3
4
5
6
7
8
(wt. %)
XX. XXX
=========
Figure B-94. Form QC-40, quality control total carbon.
-------
Appendix B
Revision 0
Date: 8/90
Page 101 of 103
Form f QC-41
Parameter - N_TOT
Total Nitrogen
Batch # Lab Code
Submission # Date Analysis Started
Run # Date Analysis Completed
Date Form Completed
Re-Analysis _ Lab Manager Initials
j Replicate Data
A ~ B ~ C D E F G
Samp. Sample Factor Inst. Blk. Inst Calculated SD
# Wt. (counts Reading Reading Result or
(ug) ug-wt%) (counts) (counts) (wt %) %RSD
XXXXXX XX.XXX XXXXXXXXXX XXXXX XX.XXX XXX.XX
'SSSSSSSSSSSSSS
Matrix Spikes
ABCDE F G H I
Samp. Sample Cone. Spike Factor Inst. Blank Spike Spike
# Wt. Spike Added Reading Inst. plus Recovery
Added (count/ Reading Sample
(ug) (wt %) (ug) ug-wt%) (counts) (count) (wt %) (%)
XXXXXX XX.XXX XXXXX XX.XXX XXXXXXXXXX XXXXX XX.XXX XXX.XX
=== ======= ======== ========
:================== ==================
QCCS (wt. %) DL-QCCS (wt. %) Calib. (wt. %)
xx.xxx xx.xxx Blank xx.xxx
True True CBLK 1
Low Low CBLK 2
High High CBLK 3
QCCS 1 Meas. CBLK 4
QCCS 2 =================== CBLK 5
QCCS 3 CBLK 6
QCCS 4 CBLK 7
QCCS 5 CBLK 8
QCCS 6 ========:
QCCS 7
QCCS 8
Figure B-95. Form QC-41, quality control total nitrogen.
-------
Appendix B
Revision 0
Date: 8/90
Page 102 of 103
Form f 42
Batch #
Submission
Run #
Re-Analysis _
Parameter - S_TOT
Total Sulfur
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
A
Samp.
1
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
B
Sample
Wt.
(g)
X . XXXX
c
Inst.
Reading
(wt %)
XX . XXXXX
D
Blk. Inst.
Reading
(wt %)
XX. XXXXX
E
Calculated
Result
(wt %)
xx . xxx
Figure B-96. Form 42, total sulfur.
-------
Appendix B
Revision 0
Date: 8/90
Page 103 of 103
Form # QC-42
Batch # _
Submission #
Run #
Re-Analysis _
Parameter - S_TOT
Total Sulfur
Lab Code
Date Analysis Started
Date Analysis Completed
Date Form Completed
Lab Manager Initials
Replicate Data
A
Samp.
#
— ==——
S£±=SS=
=:ss:===
B
Sample
Wt.
(g)
x . xxxx
=:S===3S==
c
Inst.
Reading
(wt %)
xx.xxxxx
==========
D
Blk. Inst.
Reading
(wt %)
xx.xxxxx
==s2S===s==a
E .
Calculated
Result
(wt %)
XX. XXX
==========
F
SD
or
%RSD
XXX. XX
=======3===
| Matrix Spikes
A
Samp.
f
=====
B
Sample
Wt.
(g)
X . XXXX
========
c
Cone.
Spike
Added
(wt %)
XX . XXX
======
D
Spike
Added
(g)
XX. XXXX
=======
E
-Inst.
Reading
(wt %)
xx.xxxxx
—====;===
========
F
Blank
Inst.
Reading
(wt %)
xx.xxxxx
========
G
Spike
plus
Sample
(wt %)
xx. xxx
========
H
Spike
Recovery
XXX. XX
========
QCCS
True
Low
High
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
QCCS
1
2
3
4
5
6
7
8
(wt. %)
XX. XXX
DL-QCCS
True
Low
High
Meas.
(wt. %)
XX.XXX
Calib.
Blank
CBLK
CBLK
CBLK
CBLK
CBLK
CBLK
CBLK
CBLK 8
(wt. %)
XX.XXX
Figure B-97. Form QC-42, quality control total sulfur.
-------
-------
Appendix C
Revision 0
Date: 8/90
Page 1 of 19
Appendix C
Atomic Absorption Spectroscopy Methods
(Adapted from Section 200.0 in the Manual of
Methods for Chemical Analysis of Water and Wastes
[U.S. Environmental Protection Agency, 1983])
C.1 Overview
Metals in solution may be determined by atomic absorption spectroscopy. The method is
simple, rapid, and applicable to the determination of aluminum, calcium, iron, potassium,
magnesium, and sodium in natural surface waters.
Detection limits, sensitivity, and optimum ranges of the metals will vary with the makes and
models of atomic absorption spectrophotometers. The data listed in Table C-1, however, provide
some indication of the actual concentration ranges measurable by direct aspiration and by using
furnace techniques. In the majority of instances, the concentration range shown in the table by
direct aspiration may be extended much lower with scale expansion and conversely extended
upwards by using a less sensitive wavelength or by rotating the burner head. Detection limits by
direct aspiration may also be extended through concentration of the sample through solvent
extraction techniques. Lower concentrations may also be determined using the furnace techniques.
The concentration ranges given in Table C-1 are somewhat dependent on equipment such as the
type of spectrophotometer and furnace accessory, the energy source, and the degree of electrical
expansion of the output signal. When using furnace techniques, however, the analyst should be
cautioned that chemical reactions may occur at elevated temperatures, which may result in either
suppression or enhancement of the signal from the element being analyzed. To insure valid data,
the analyst should examine each matrix for interference effects (matrix spike analysis), and if
detected, should analyze the samples by the method of standard additions.
In direct aspiration atomic absorption spectroscopy, a sample is aspirated and atomized
in a flame. A light beam from a hollow cathode lamp, which has a cathode made of the element
to be determined, is directed through the flame into a monochromator and onto a detector that
measures the amount of light absorbed. Absorption depends on the presence of free, unexcited,
ground state atoms in the flame. Since the wavelength of the light beam is characteristic of only
the metal being determined, the light energy absorbed by the flame is a measure of atomic
absorption spectroscopy.
When using the furnace technique in conjunction with an atomic absorption
spectrophotometer, a representative aliquot of a sample is placed in the graphite tube in the
furnace, evaporated to dryness, charred, and atomized. As a greater percentage of available analyte
atoms is vaporized and dissociated for absorption in the tube than in the flame, the use of small
sample volumes or detection of low concentrations of elements is possible. The principle is
essentially the same as with direct aspiration atomic absorption, except a furnace is used to
atomize the sample instead of a flame. Radiation from a given excited element is passed through
-------
Appendix C
Revision 0
Date: 8/90
Page 2 of 19
Table C-1. Atomic Absorption Concentration Rang**'
Flame Furnace b'c
Metal
Calcium
Iron
Magnesium
Potassium
Sodium
Detection
Limit
(mg/L)
0.01
0.03
0.001
0.01
0.002
Sensitivity
(mg/L)
0.08
0.12
0.007
0.04
0.015
Optimum
Concentration
Range
(mg/L)
0.2 to 7
0.3 to 5
0.02 to 0.5
0.1 to 2
0.03 to 1
Optimum
Detection Concentration
Limit Range
(pg/L) O^g/L)
— —
1 5 to 100
—
— —
— —
* The concentrations shown are obtainable with any satisfactory atomic absorption spectrophotometer.
* For furnace sensitivity values, consult instrument operating manual.
cThe listed furnace values are those expected when using a 20-pL injection and normal gas flow.
the vapor containing ground state atoms of that element. The intensity of the transmitted radiation
decreases in proportion to the amount of the ground state element in the vapor.
The metal atoms to be measured are placed in the beam of radiation by increasing the
temperature of the furnace, thereby causing the injected specimen to be volatilized. The
monochromator isolates the characteristic radiation from the hollow cathode lamp and a
photosensitive device measures the attenuated transmitted radiation.
C.1.2 Definitions
1. Optimum concentration range-A range defined by limits expressed in concentration,
below which scale expansion should be used and above which curve correction should
be considered. This range varies with the sensitivity of the instrument and the operating
conditions employed.
2. Sensitivity-The concentration in milligrams of metal per liter that produces an absorption
of 1 percent.
3. Dissolved metals-Those constituents (metals) which can pass through a 0.45-^m
membrane filter.
4. Suspended metals-Those constituents (metals) which are retained by a 0.45-^m
membrane filter.
5. Total metals--The concentration of metals is determined on an unfiltered sample
following vigorous digestion.
6. Total recoverable metals-The concentration of metals in an unfiltered sample following
treatment with hot, dilute mineral acid.
-------
Appendix C
Revision 0
Date: 8/90
Page 3 of 19
C. 1.3 Interferences
1. Direct Aspiration-The most troublesome type of interference in atomic absorption
spectrophotometry is usually termed "chemical" and is caused by lack of absorption of
atoms bound in molecular combination in the flame. This phenomenon can occur when
the flame is not sufficiently hot to dissociate the molecule, as in the case of phosphate
interference with magnesium, or because the dissociated atom is immediately oxidized
to a compound that will not dissociate further at the temperature of the flame. The
addition of lanthanum will overcome the phosphate interference in the magnesium and
calcium determinations. While complexing agents are primarily employed to increase the
sensitivity of the analysis, they may also be used to eliminate or reduce interferences.
Chemical interferences may also be eliminated by separating the metal from the
interfering material.
The presence of high dissolved solids in the sample may result in an interference from
non-atomic absorbance such as light scattering. If background correction is not available,
a non-absorbing wavelength should be checked. Preferably, high solid type samples
should be extracted.
lonization interferences occur when the flame temperature is sufficiently high to generate
the removal of an electron from a neutral atom, giving a positively charged ion. This type
of interference can generally be controlled by the addition, to both standard and sample
solutions, of a large excess of an easily ionized element.
Although quite rare, spectral interference can occur when an absorbing wavelength of an
element present in the sample, but not being determined, falls within the width of the
absorption line of the element of interest. The results of the determination will then be
erroneously'high, due to the contribution of the interfering element to the atomic
absorption signal. Also, interference can occur when resonant energy from another
element in a multielement lamp or a metal impurity in the lamp cathode falls within the
bandpass of the slit setting, and that metal is present in the sample. This type of
interference may sometimes be reduced by narrowing the slit width.
2. Flameless Atomization-Although the problem of oxide formation is greatly reduced with
furnace procedures because atomization occurs in an inert atmosphere, the technique
is still subject to chemical and matrix interferences. The composition of the sample
matrix can have a major effect on the analysis. It is this effect which should be
determined and taken into consideratio in the analysis of each different matrix
encountered. To verify the absence of matrix or chemical interference, a matrix spike
sample is analyzed using the following procedure:
a. Withdraw two equal aliquots from the sample.
b. Add a known amount of analyte and dilute both aliquots to the same predetermined
volume. The dilution volume should be based on the analysis of the undiluted sample.
Preferably, the dilution should be 1:4 while keeping in mind the optimum concentration
range of the analysis. Under no circumstances should the dilution be less than 1:1.
c. Analyze the diluted aliquots.
-------
Appendix C
Revision 0
Date: 8/90
Page 4 of 19
d. Multiply the unspiked results by the dilution factor and compare to the original
determination.
Agreement of the results (within ±10 percent) indicates the absence of interference.
Comparison of the actual signal from the spike to the expected response from the analyte
in an aqueous standard helps confirm the finding from the dilution analysis. Those
samples which indicate the presence of interference should be analyzed by the method
of standard additions.
Gases generated in the furnace during atomization may have a molecular absorption band
encompassing the analytical wavelength. When this occurs, either the use of background
correction or selection of an alternate wavelength outside the absorption band should
eliminate this interference. Background correction can also compensate for non-specific
broadband absorption interference.
Interference from a smoke-producing sample matrix can sometimes be reduced by
extending the charring time at a higher temperature or utilizing an ashing cycle in the
presence of air. Care should be taken, however, to prevent loss of the element being
analyzed.
Samples containing large amounts of organic materials should be oxidized by conventional
acid digestion prior to being placed in the furnace. In this way, broad band absorption
will be minimized.
From anion interference studies in the graphite furnace, it is generally accepted that nitric
acid is preferable for any digestion of the solubilization step. If another acid in addition
to HN03 is required, a minimum amount should be used. This applies particularly to
hydrochloric and to a lesser extent, to sulfuric and phosphoric acids.
Carbide formation resulting from the chemical environment of the furnace has been
observed with certain elements that form carbides at high temperatures. Molybdenum is
an example. When this takes place, the metal will be released very slowly from the
carbide as atomization continues. For molybdenum, atomization for 30 seconds or more
may be required before the signal returns to baseline levels. This problem is greatly
reduced, and the sensitivity is increased with the use of prolytically-coated graphite.
C.1.4 Safety
The calibration standards, sample types, and most reagents pose no hazard to the analyst.
Protective clothing (laboratory coat and gloves) and safety glasses should be worn when preparing
reagents, especially when concentrated acids and bases are used. The use of concentrated
hydrochloric acid and ammonium hydroxide solutions should be restricted to a fume hood.
Follow the manufacturer's safety precautions when operating the atomic absorption
spectrophotometers. Chain or bolt compressed gas cylinders in an upright position.
-------
Appendix C
Revision 0
Date: 8/90
Page 5 of 19
C.2 Sample Collection, Preservation, and Storage
For the determination of trace metals, contamination and loss are of prime concern. Dust
in the laboratory environment, impurities in reagents, and impurities on laboratory apparatus which
the sample contacts are all sources of potential contamination. For liquid samples, containers can
introduce either positive or negative errors in the measurement of trace metals by (a) contributing
contaminants through leaching or surface desorption, and by (b) depleting concentrations through
absorption. Thus, the collection and treatment of the sample prior to analysis requires particular
attention. The sample bottle, whether borosilicate glass, polyethylene, polypropylene, or Teflon,
should be thoroughly washed with detergent and tap water, should be rinsed with 1:1 nitric acid, tap
water, 1:1 hydrochloric acid, tap water, and finally with deionized, distilled water (in that order).
NOTE 1: Chromic acid may be used to remove organic deposits from glassware; however,
the analyst should be cautioned that the glassware must be thoroughly rinsed
with water to remove the last traces of chromium. This is especially important
if chromium is to be included in the analytical scheme. A commercial product-
NOCHROMIX-available from Godax Laboratories, 6 Varick St., New York, NY
10013, may be used in place of chromic acid. (Chromic acid should not be used
with plastic bottles.)
NOTE 2: If it can be documented through an active analytical quality control program using
spiked samples, reagent blanks and sample blanks, that certain steps in the
cleaning procedure are not required for routine samples, those steps might be
eliminated from the procedure. Before collection of the sample, a decision must
be made as to the type of data desired, i.e., dissolved, suspended, total, or total
recoverable. Drinking water samples containing suspended and settleable
material should be prepared by using the total recoverable metal procedure.
For the determination of dissolved constituents, the sample must be filtered through a 0.45-
/jm membrane filter as soon as practical after collection. (Glass or plastic filtering apparatus using
plain, non-grid marked, membrane filters are recommended to avoid possible contamination.) Use
the first 50-100 mL to rinse the filter flask. Discard this portion and collect the required volume of
filtrate. Acidify the filtrate with 1:1 redistilled HNO3 to a pH of <2. Normally, 3 ml of (1:1) acid per
liter should be sufficient to preserve the sample (see Note 3). If hexavalent chromium is to be
included in the analytical scheme, a portion of the filtrate should be transferred before acidification
to a separate container and should be analyzed as soon as possible. Analyses performed on a
sample so treated shall be reported as "dissolved" concentrations.
NOTE 3: If a precipitate is formed upon acidification, the filtrate should be digested. Also,
it has been suggested (International Biological Program, Symposium on Analytical
Methods, Amsterdam, October 1966) that additional acid, as much as 25 mL of
concentrated HCI per liter, may be required to stabilize certain types of highly
buffered samples if they are to be stored for any length of time. Therefore,
special precautions should be observed for preservation and storage of unusual
samples intended for metal analysis.
For the determination of suspended metals a representative volume of unpreserved sample
must be filtered through a 0.45-pm membrane filter. When considerable suspended material is
present, as little as 100 mL of a well mixed sample is filtered. Record the volume filtered and
transfer the membrane filter containing the insoluble material to a 250-mL Griffin beaker and add
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3 mL concentrated redistilled HNO3. Cover the beaker with a watch glass and heat gently. The
warm acid will soon dissolve the membrane. Increase the temperature of the hot plate and digest
the material. When the acid has nearly evaporated, cool the beaker and watch glass and add
another 3 ml of concentrated, redistilled HNO3. Cover and continue heating until the digestion is
complete; generally complete digestion is indicated by a light colored residue. Evaporate to near
dryness (do not bakd), add 5 mL distilled HCI (1:1), and warm the beaker gently to dissolve any
soluble material. (If the sample is to be analyzed by the furnace procedure, 1 mL of 1:1 distilled
HNO3 per 100 mL dilution should be substituted for the distilled 1:1 HCI.) Wash down the watch
glass and beaker walls with deionized, distilled water and filter the sample to remove silicates and
other insoluble material that could clog the atomizer. Adjust the volume to some predetermined
value based on the expected concentrations of metals present. This volume will vary depending on
the metal to be determined. The sample is now ready for analysis. Concentrations so determined
shall be reported as "suspended." (See Note 4.)
NOTE 4: Certain metals such as antimony, arsenic, gold, iridium, mercury, osmium,
palladium, platinum, rhenium, rhodium, ruthenium, selenium, silver, thallium, tin,
and titanium require modification of the digestion procedure, and the individual
sheets for these metals should be consulted.
For the determination of total metals the sample is acidified with 1:1 redistilled HNO3 to a
pH of 2 at the time of collection. The sample is not filtered before processing. Choose a volume
of sample appropriate for the expected level of metals. If much suspended material is present, as
little as 50-100 mL of well mixed sample will probably be sufficient. (The sample volume required
may also vary proportionally with the number of metals to be determined.) Transfer a representative
aliquot of the well mixed sample to a Griffin beaker and add 3 mL of concentrated redistilled HNO3.
Place the beaker on a hot plate and evaporate to dryness cautiously, making certain that the sample
does not boil, (do not bake) Cool the beaker and add another 3 mL portion of concentrated,
redistilled HNO3. Cover the beaker with a watch glass and return the beaker to the hot plate.
Increase the temperature of the hot plate so that a gentle reflux action occurs. Continue heating
and add additional acid as necessary until the digestion is complete (generally indicated by a light
colored residue or by no change in appearance with continued refluxing). Again, evaporate to near
dryness and cool the beaker. Add a small quantity of redistilled 1:1 HCI (5 mL/100 mL of final
solution) and warm the beaker to dissolve any precipitate or residue resulting from evaporation. (If
the sample is to be analyzed by the furnace procedure, substitute distilled HNO3 for 1:1 HCI so that
the final dilution contains 0.5% (v/v) HNOJ. Wash down the beaker walls and watch glass with
distilled water and filter the sample to remove silicates and other insoluble material that could clog
the atomizer. Adjust the volume to some predetermined value based on the expected metal
concentrations. The sample is now ready for analysis. Concentrations so determined shall be
reported as "total." (See Note 4.)
To determine total recoverable metals, acidify the entire sample at the time of collection with
concentrated, redistilled HNO3, 5 mL/L. At the time of analysis, a 100-mL aliquot of well mixed
sample is transferred to a beaker or flask. Five mL of distilled HCI (1:1) is added, and the sample
is heated on a steam bath or hot plate until the volume has been reduced to 15 to 20 mL; be certain
that the samples do not boil. (If the sample is being prepared for furnace analysis, the same
process should be followed except HCI should be omitted.) After this treatment the sample is filtered
to remove silicates and other insoluble material that could clog the atomizer, and the volume is
adjusted to 100 mL. The sample is then ready for analysis. Concentrations so determined shall be
reported as "total". (See notes 4, 5, and 6.)
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NOTES: The analyst should be cautioned that this digestion procedure may not be
sufficiently vigorous to destroy certain metal complexes if a calorimetric procedure
is to be employed for the final determination. When this is suspected, the more
vigorous digestion should be used.
NOTE 6: For drinking water analyses by direct aspiration, the final volume may be reduced
to effect up to a 10x concentration of the sample if the total dissolved solids in
the original sample do not exceed 500 mg/L The determination is corrected for
any nonspecific absorbance, and there is not loss by precipitation.
C.3 Equipment and Supplies
C.3.1 Equipment and Apparatus
1. Atomic absorption spectrophotometer-The required spectrophotometer is a single- or
dual-channel, single- or double-beam instrument having a grating monochromator,
photomultiplier detector, adjustable slits, a wavelength range of 190 to 800 nm, and
provisions for interfacing with a strip chart recorder.
2. Burner-The burner recommended by the particular instrument manufacturer should be
used. For certain elements, a nitrous oxide burner is required.
3. Hollow cathode lamps-Single element lamps are preferred, but multielement lamps may
be used. Electrodeless discharge lamps may also be used when available.
4. Graphite furnace-Any furnace device capable of reaching the specified temperatures is
satisfactory.
5. Strip chart recorder-A recorder is recommended for furnace work so that there will be
a permanent record and so that any problems with the analysis (i.e., drift, incomplete
atomization, losses during charring, changes in sensitivity) can be recognized easily.
C.3.2 Reagents and Consumable Materials
General reagents used in each metal determination are listed in this section. Reagents
specific to particular metal determinations are listed in the particular procedure description for that
metal.
1. Concentrated hydrochloric acid (12M HCI)-Ultrapure grade (Baker Instra-Analyzed or
equivalent).
2. HCI (1 percent v/v)--Add 5 mL of concentrated HCI to 495 ml_ deionized, distilled water.
3. Nitric acid (0.5% v/v) HNO3--Carefully dilute Ultrapure grade HNO3 (Baker Instra-Analyzed
or equivalent) in deionized, distilled water in the ratio of 0.5 to 100.
4. Stock standard metal solutions-Prepare as directed in the individual metal procedures.
Commercially available stock standard solutions may also be used.
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5. Dilute calibration standards-Prepare a series of standards of the metal by dilution of
the appropriate stock metal solution to cover the concentration range desired.
6. Fuel and oxidant-Commercial grade acetylene is generally acceptable. Air may be
supplied from a compressed air line, a laboratory compressor, or from a cylinder of
compressed air. Reagent grade nitrous oxide is required for certain determinations.
Standard, commercially available argon and nitrogen are required for furnace work.
7. Water-Water should meet the specifications for Type I reagent grade water (American
Society for Testing and Materials [ASTM], 1984).
C.4 Calibration and Standardization
The calibration procedure varies slightly with the various atomic absorption instruments.
For each analyte, calibrate the atomic absorption instrument by analyzing a calibration blank and
a series of standards; follow the instructions in the instrument operating manual. The concentration
of standards should bracket the expected sample concentration; however, the linear range of the
instrument should not be exceeded.
When indicated by the matrix spike analysis, the analytes should be quantified by the
method of standard additions. In this method, equal volumes of sample are added to a deionized
water blank and to three standards containing different known amounts of the test element. The
volume of the blank and of each standard should be the same. The absorbance of each solution
is determined and then plotted on the vertical axis of a graph, with the concentrations of the known
standards plotted on the horizontal axis. When the resulting line is extrapolated to zero absorbance,
the point of intersection of the abscissa is the concentration of the unknown. The abscissa on the
left of the ordinate is scaled the same as on the right side, but in the opposite direction from the
ordinate. (See Figure C-1). The method of standard additions can be very useful; however, for the
results to be valid, the following limitations should be taken into consideration:
1. The absorbance plot of sample and standards should be linear over the concentration
range of concern. For best results, the slope of the plot should be nearly the same as
the slope of the aqueous standard curve. If the slope is significantly different (more
than 20 percent), caution should be exercised.
2. The effect of the interference should not vary as the ratio of analyte to sample matrix
changes, and the standard addition should respond in a similar manner as the analyte.
3. The determination should be free of spectral interference and corrected for nonspecific
background interference.
C.5 Quality Assurance and Quality Control
C.5.1 Precision and Accuracy
1. Determination of Dissolved Calcium-
In a single laboratory (U.S. Environmental Protection Agency (EPA) Environmental
Monitoring Systems Laboratory [EMSL]-Cincinnati) using distilled water spiked at
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concentrations of 9.0 and 36 mg/L Ca2+, the standard deviations were ±0.3 and ±0.6,
respectively. Recoveries at both these levels were 99 percent.
2. Determination of Dissolved Iron-
An interlaboratory study on trace metal analyses by atomic absorption was conducted by
the Quality Assurance and Laboratory Evaluation Branch of EMSL-Cincinnati. Six synthetic
concentrates containing varying levels of aluminum, cadmium, chromium, copper, iron,
manganese, lead, and zinc were added to natural water samples. The statistical results
for iron were as follows:
Number
of Labs
82
85
79
78
57
54
True Value
(MO/L)
Mean Value
Standard
Deviation
840
700
438
350
24
10
855
680
435
348
58
48
173
178
183
131
69
69
Accuracy as
Percent Bias
18
-2,8
-0.7
-0.5
141
382
Absorbance or
Emission
Zero Absorbance/
Emission
Concentration
Cone, of Addn 0 Addn 1 Addn 2 •• Addn 3
Sample No Addn Addn of 50% Addn of 100% Addn of 150%
of Expected of Expected of Expected
Amount Amount Amount
Figure C-1. Standard additions plot
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3. Determination of Dissolved Magnesium--
In a single laboratory (EMSL-Cincinnati), using distilled water spiked at concentrations
of 2.1 and 8.2 mg/L Mg2+, the standard deviations were ±0.1 and ±0.2, respectively.
Recoveries at both of these levels were 100 percent.
4. Determination of Dissolved Potassium-
In a single laboratory (EMSL-Cincinnati), using distilled water samples spiked at
concentrations of 1.6 and 6.3 mg/L K+, the standard deviations were ±0.2 and ±0.5,
respectively. Recoveries at these levels were 103 percent and 102 percent, respectively.
5. Determination of Dissolved Sodium-
In a single laboratory (EMSL-Cincinnati), using distilled water samples spiked at levels
of 8.2 and 52 mg/L Na+, the standard deviations were ±0.1 and ±0.8, respectively.
Recoveries at these levels were 102 percent and 100 percent.
C.5.2 Quality Control
Minimum requirements-
1. All quality control data should be maintained and should be available for easy reference
or inspection.
2. An unknown performance sample (when available) must be analyzed once per year for
the metals measured. Results must be within the control limits established by EPA.
If problems arise, they should be corrected, and a follow-up performance sample should
be analyzed.
Minimum Daily Control-
1. After a calibration curve composed of a minimum of a reagent blank and three
standards has been prepared, subsequent calibration curves must be verified by use of
at least a reagent blank and one standard at or near the instrument detection limit
(IDL). Daily checks must be within ±10 percent of original curve.
2. If 20 or more samples per day are analyzed, the working standard curve must be
verified by running an additional standard at or near the IDL every 20 samples. Checks
must be within ±10 percent of the original curve.
Optional Requirements-
1. A current service contract should be in effect on balances and on the atomic absorption
spectrophotometer.
2. Class "S" weights should be available to make periodic checks on balances.
3. Chemicals should be dated upon receipt of shipment and replaced as needed or before
shelf life has been exceeded.
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4. A known reference sample (when available) should be analyzed once per quarter for the
metals measured. The measured value should be within the control limits.
5. At least one duplicate sample should be run every 10 samples or with each set of
samples to verify precision of the method. Checks should be within the control limits
established by EPA.
6. Standard deviations should be obtained and documented for all measurements being
conducted.
7. Quality control charts or a tabulation of means and standard deviations should be used
to document validity of data on a daily basis.
C.6 Procedure
C.6.1 Flame Atomic Absorption Spectroscopy
Differences among the various makes and models of satisfactory atomic absorption
spectrophotometers prevent the formulation of detailed instructions applicable to every instrument.
The analyst should follow the manufacturer's operating instructions for a particular instrument. In
general, after choosing the proper hollow cathode lamp for the analysis, the lamp should be allowed
to warm up for a minimum of 15 minutes unless operated in a double-beam mode.
During this period, align the instrument, position the monochromator at the correct
wavelength, select the proper monochromator slit width, and adjust the hollow cathode current
according to the manufacturer's recommendation. Subsequently, light the flame and regulate the
flow of fuel and oxidant, adjust the burner and nebular flow rate for maximum percent absorption
and stability, and balance the photometer. Run a series of standards of the element under analysis
and calibrate the instrument. Aspirate the samples and determine the concentrations either directly
(if the instrument reads directly in concentration units) or from the calibration curve.
C. 6.2. Furnace A tomic Absorption Spectroscopy
Furnace devices (flameless atomization) are a useful means of extending detection limits.
Because of differences among various makes and models of satisfactory instruments, no detailed
operating instructions can be given for each instrument. Instead, the analyst should follow the
instructions provided by the manufacturer of a particular instrument. The following points may be
helpful:
1. With flameless atomization, background correction is important, especially below 350
nm. This is because certain samples, when atomized, may absorb or scatter light from
the hollow cathode lamp. These effects can be caused by the presence of gaseous
molecular species, salt particles, or smoke in a sample beam. If no correction is made,
sample absorbance will be greater than it should be, and the analytical result will be
erroneously high.
2. If all of the analyte is not volatilized during atomization and removed from the furnace,
memory effects will occur. This condition depends on several factors (i.e., the volatility
of the element and its chemical form, whether pyrolytic graphite is used, the rate of
atomization, and furnace design). If this situation is detected through blank burns, the
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tube should be cleaned by operating the furnace at full power for the required time
period at regular intervals in the analytical scheme.
3. Some of the smaller furnace devices, or newer furnaces equipped with feedback
temperature control (Instrumentation Laboratories Model 555, Perkin-Elmer Models HGA
220 and HGA 76B, and Barian Model CRA-90) employing faster rates of atomization, can
be operated using lower atomization temperatures for shorter time periods than those
listed in this method.
4. In many cases, prior digestion of the sample is not required if a representative aliquot
of sample can be pipetted into the furnace. However, prior digestion provides a more
uniform matrix and possibly lessens matrix effects.
5. Inject a measured microliter aliquot of the sample into the furnace and atomize. If the
concentration found is greater than the highest standard, the sample should be diluted
in the same acid matrix and reanalyzed. The use of multiple injections can improve
accuracy and can help detect furnace pipetting errors.
C.6.3 Procedure for Determination of Dissolved Calcium
Samples for determination of dissolved calcium are analyzed by flame atomic absorption
spectroscopy for calcium (U.S. EPA, 1983).
1. Preparation of lanthanum chloride matrix modifier solution (LaCy-Dissolve 29 g of
La2O3. slowly and in small portions, in 250 ml of concentrated HCI (Caution: reaction
is violent) and dilute to 500 mL with deionized, distilled water.
2. Preparation of calcium standard solutions-
a. Calcium stock solution (500 mg/L Ca24)-Suspend 1.250 g of CaCO3 (analytical
reagent grade, dried at 180 °C for 1 hour before weighing in water and dissolved
cautiously with a minimum of dilute HCI). Dilute to 1,000 mL with deionized, distilled
water.
b. Dilute calibration standards-Each day, quantitatively prepare a series of dilute Ca2+
standards from the calcium stock solution to span the desired concentration range.
3. Suggested Instrumental Conditions (General)-
a. Lamp~Ca2*, hollow cathode.
b. Wavelength~422.7 nm.
NOTE: The 239.9 nm line may also be used. This line has a relative sensitivity of 120.
c. Fuel-acetylene.
d. Oxidant-air.
e. Flame-reducing.
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4. Analysis Procedure--
a. To each 10.0-mL volume of dilute calibration standard, blank, and sample add 1.00 ml
of LaCI3 solution (e.g., add 2.0 ml of LaCI3 solution to 20.0 ml of sample).
b. Calibrate the instrument as directed by the manufacturer.
c. Analyze the samples, including quality control (QC) samples.
d. Dilute and reanalyze any samples with a concentration exceeding the calibrated range.
e. Report results as mg/L Ca2+.
NOTE 1: Phosphate, sulfate, and aluminum interfere but are masked by the addition of lanthanum.
Because low calcium values result if the pH of the sample is above 7, both standards
and samples are prepared in dilute acid solution. Concentrations of magnesium greater
than 1,000 mg/L also cause low calcium values. Concentrations of up to 500 mg/L each
of sodium, potassium, and nitrate cause no interference.
NOTE 2: Anionic chemical interferences can be expected if lanthanum is not used in samples and
standards.
NOTE 3: The nitrous oxide-acetylene flame will provide two to five times greater sensitivity and
freedom from chemical interferences. lonization interferences should be controlled by
adding a large amount of alkali to the sample and standards. The analysis appears to
be free from chemical suppressions in the nitrous oxide-acetylene flame.
C.6.4 Procedure for Determination of Dissolved Iron
The samples for determination of dissolved iron are analyzed by flame atomic absorption
spectroscopy (U.S. EPA, 1983).
1. Preparation of iron standard solutions-
a. Iron stock solution (1,000 mg/L Fe3+)--Carefully weigh 1.000 g of pure iron wire (analytical
reagent grade) and dissolve in 5 mL of concentrated HNO3, warming if necessary. When
iron is completely dissolved, bring the volume of the solution to 1 L with deionized,
distilled water.
b. Dilute calibration standards-Each day, quantitatively prepare a series of calibration
standards spanning the desired concentration range. Match the acid content of the
standards to that of the samples (ca. 0.1 percent (v/v)
2. Suggested Instrumental Conditions (General)--
a. Lamp~Fe3+, hollow cathode.
b. Wavelength~248.3 nm.
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NOTE: The following lines may also be used: 248.8 nm, relative sensitivity 2; 271.9 nm, relative
sensitivity 4; 302.1 nm, relative sensitivity 5; 252.7 nm, relative sensitivity 6; 372.0 nm,
relative sensitivity 10.
c. Fuel-acetylene.
d. Oxidant-air.
e. Flame-oxidizing.
3. Analysis Procedure--
a. Calibrate the instrument as directed by the instrument manufacturer.
b. Analyze the samples.
c. Dilute and reanalyze any samples with a concentration exceeding the calibrated range.
d. Report results in mg/L Fe3*.
C.6.5 Procedure for Determination of Dissolved Magnesium
The samples for determination of dissolved magnesium are analyzed by flame atomic
absorption spectroscopy.
1. Preparation of lanthanum chloride matrix modifier solution (LaCy-Dissolve 29 g of
La2O3, slowly and in small portions, in 250 mL concentrated HCI (Caution: reaction is
violent), and dilute to 500 mL with deionized, distilled water.
2. Preparation of magnesium standard solutions-
a. Stock solution (500 mg/L Mg)-Dissolve 0.829 g of magnesium oxide (MgO, analytical
reagent grade) in 10 mL of HNO3 and dilute in 1 L with water.
b. Dilute calibration standards-Each day, quantitively prepare from the Mg stock solution
a series of Mg2+ standards that span the desired concentration range.
3. Suggested Instrumental Conditions (General)-
a. Lamp~Mg2+, hollow cathode.
b. Wavelength-285.2 nm.
NOTE: The line at 202.5 nm may also be used. This line has a relative sensitivity of 25.
c. Fuel-acetylene.
d. Oxidant-air.
e. Flame-oxidizing.
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4. Analysis Procedure-
a. To each 10.0 mL of dilute calibration standard, blank, and sample, add 1.00-mL of
LaCI3 solution (e.g., add 2.0 mL LaCI3 solution to 20.0 ml of sample).
b. Calibrate the instrument as directed by the manufacturer.
c. Analyze the samples.
d. Dilute and reanalyze any samples with a concentration exceeding the linear range.
e. Report results as mg/L Mg2+.
NOTE 1: The interference caused by aluminum at concentrations greater than 2 mg/L is masked
by additional lanthanum. Sodium, potassium, and calcium cause no interference at
concentrations less than 400 mg/L.
NOTE 2: To cover the range of magnesium values normally observed in surface waters (0.1 to 20
mg/L), it is suggested that either the 202.5-nm line be used or that the burner head be
rotated. A 90° rotation of the burner head will produce approximately one-eighth the
normal sensitivity.
C.6.6 Procedure for Determination of Dissolved Potassium
The samples for determination of dissolved potassium are analyzed by flame atomic
absorption spectroscopy (U.S. EPA, 1983).
1. Preparation of potassium standard solutions-
a. Potassium stock solution (100 mg/L K+)~Dissolve 0.1907 g of KCI (analytical reagent
grade, dried at 110 °C) in deionized, distilled water and bring the volume of the
solution to 1 L.
b. Dilute calibration standards-Each day, quantitatively prepare a series of calibration
standards spanning the desired concentration range. Match the acid content of the
standards to that of the samples (ca. 0.1 percent (v/v) HNOJ.
2. Suggested Instrumental Conditions (General)--
a. Lamp~K+, hollow cathode.
b. Wavelength-766.5.
NOTE: The line at 404.4 nm may also be used. This line has a relative sensitivity of 500.
c. Fuel-acetylene.
d. Oxidant-air.
e. Flame-slightly oxidizing.
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3. Analysis Procedure-
a. Calibrate the instrument as directed by the manufacturer.
b. Analyze the samples.
c. Dilute and reanalyze any samples with a concentration exceeding the calibrated range.
d. Report results as mg/L K+.
NOTE 1: In air-acetylene or other high-temperature flames (greater than 2,800 °C), potassium can
experience partial ionization which indirectly affects absorption sensitivity. The presence
of other alkali salts in the sample can reduce this ionization suppressive effect and
thereby enhance analytical results. The ionization suppressive effect of sodium is small
if the ratio of Na+ to K+ is under 10. Any enhancement due to sodium can be stabilized
by adding excess sodium (1,000 pg/mL) to both sample and standard solutions. If more
stringent control of ionization is required, the addition of cesium should be considered.
Reagent blanks should be analyzed to correct for potassium impurities in the buffer
stock.
NOTE 2: To cover the range of potassium values normally observed in surface waters (0.1 to 20
mg/L), it is suggested that the burner head be rotated. A 90° rotation of the burner
head provides approximately one-eighth the normal sensitivity.
C.6.7 Procedure for Determination of Dissolved Sodium
The samples for determination of dissolved sodium are analyzed by flame atomic absorption
spectroscopy for sodium (U.S. EPA, 1983).
1. Preparation of sodium standard solutions-
a. Sodium stock solution (1,000 mg/L Na4)--Dissolve 2.542 g of NaCI (analytical reagent
grade, dried at 140 °C) in deionized, distilled water and bring the volume of the
solution to 1 L
b. Dilute calibration standards-Each day, quantitatively prepare a series of calibration
standards spanning the desired concentration range. Match the acid content of the
standards to that of the samples (ca. 0.1 percent (v/v) HNOJ.
2. Suggested Instrumental Conditions (General)--
a. Lamp~Na+, hollow cathode.
b. Wavelength-589.6 nm.
NOTE: The 330.2 nm resonance line of sodium, which has a relative sensitivity of 185, provides
a convenient way to avoid the need to dilute more concentrated solutions of sodium.
c. Fuel-acetylene.
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d. Oxidant~air.
e. Flame-oxidizing.
3. Analysis Procedure--
a. Calibrate the instrument as directed by the manufacturer.
b. Analyze the samples.
c. Dilute and reanalyze any samples with a concentration exceeding the calibrated range.
d. Report results as mg/L Na+.
NOTE: Low-temperature flames increase sensitivity by reducing the extent of ionization of this
easily ionized metal. Ionization may also be controlled by adding potassium (1000 mg/L)
to both standards and samples.
C.6.8 Direct Aspiration
Generally, instruments are calibrated to give sample results directly in concentration units.
For those instruments which do not read out directly in concentration, a calibration curve is prepared
to cover the appropriate concentration range. Usually, this means the preparation of standards
which produce an absorption of 0 to 80 percent. The correct method is to convert the percent
absorption readings to absorbance and to plot that value against concentration. The following
relationship is used to convert absorption values to absorbance:
absorbance = log (100 + %T) = 2 - log % T
where: % T = 100 - % absorption
As the curves are frequently nonlinear, especially at high absorption values, the number of
standards should be increased in that portion of the curve.
1. Direct determination of liquid samples: Read the metal value in mg/L from the
calibration curve or directly from the readout system of the instrument. If dilution of
sample was required:
mg/L metal in sample = A [(C + B) •*• C]
where: A = mg/L of metal in diluted aliquot from calibration curve
B = mL of deionized, distilled water used for dilution
C = mL of sample aliquot
2. For samples containing particulates:
mg/L metal in sample = A (V + C)
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where: A = mg/L of metal in processed sample from calibration curve
V = final volume of the processed sample in mL
C - ml_ of sample aliquot processed
3. For solid sample: report all concentrations as mg/kg dry weight:
mg metal/kg sample = (A x V) + D
where: A = mg/L of metal in processed sample from calibration curve
V = final volume of the processed sample in ml
D = weight of wet sample in grams
C.6.9 Furnace Calculations
For determination of metal concentration by the furnace method. Read the metal value in
/jg/L from the calibration curve or directly from the readout system of the instrument.
1. If different size furnace injection volumes are used for samples than for standards:
pg/L of metal in sample = Z (S •*• U)
where: Z = jug/L of metal from calibration curve or readout system
S = n\. volume standard injected into furnace for calibration curve
U = yL volume of sample injected for analysis
2. If dilution of sample was required, and if sample injection volume is the same as for the
standard:
pg/L of metal in sample = Z [(C + B) + C]
where: Z = pg/L metal in diluted aliquot from calibration curve
B = ml of deionized, distilled water used for dilution
C = mL of sample aliquot
3. For samples containing particulates:
of metal in sample = Z (V + C)
where: Z = /jg/L of metal in processed sample from calibration curve
V = final volume of processed sample in mL
C = mL of sample aliquot processed
4. For solid samples: Report all concentrations as mg/kg dry weight.
4a. Dry sample:
mg metal/kg sample = (Z x V) + 1,0000
where: Z = jug/L of metal in processed sample from calibration curve
V = final volume of processed sample in mL
D = weight of dry sample in grams
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4b. Wet sample:
mg metal/kg sample =(ZxV)-s-(WxPx 1,000)
where: Z = pg/L of metal in processed sample from calibration curve
V = final volume of processed sample in mL
W = weight of dry sample in grams
P = % solids
C.7 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specification for Reagent Water, D 1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
U.S. Environmental Protection Agency. 1983 (revised). Methods for Chemical Analysis of Water and
Wastes. EPA 600/4-79-020. U.S. Environmental Protection Agency, Cincinnati, Ohio.
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Appendix D
Inductively Coupled Plasma Atomic Emission Spectrometric
Method for Trace Element Analyses of Water and Wastes
(Adapted from Method 200.7 in the Manual for Chemical
Analysis of Water and Wastes
[U.S. Environmental Protection Agency, 1983])
D.1 Overview
This method may be used for the' determination of dissolved, suspended, or total elements in
drinking water, surface water, and domestic and industrial waste waters. Dissolved elements are
determined in filtered and acidified samples. Appropriate steps must be taken in all analyses to
ensure that potential interferences are taken into account. This is especially true when dissolved
solids exceed 1,500 mg/L Total elements are determined after appropriate digestion procedures are
performed. Since digestion techniques increase the dissolved solids content of the samples,
appropriate steps must be taken to correct for potential interference effects.
Table D-1 lists the recommended wavelengths and typical estimated instrumental detection
limits using conventional pneumatic nebulization for the specific elements analyzed by inductively
coupled argon plasma (ICP) in the Direct/Delayed Response Project (DDRP) (see sections 12,13,14,
and 16). Actual working detection limits are sample-dependent and as the sample matrix varies,
these concentrations may also vary. In time, other elements may be added as more information
becomes available, and as required.
Table D-1. Recommended Wavelengths and Estimated Instrumental Detection Limits
Element Wavelength (nm)tf Estimated detection limit (pg/L)
b
Aluminum 308.215 45
Calcium 317.933 10
Iron 259.940 7
Magnesium 279.079 30
Silicon . 288.158 58
' The wavelengths listed are recommended because of their sensitivity and overall acceptance. Other wavelengths may
be substituted if they can provide the needed sensitivity and are treated with the same corrective techniques for spectral
interference.
The estimated instrumental detection limits as shown are taken from Fassel (1982). They are given as a guide for an
instrumental limit. The actual method detection limits are sample-dependent and may vary as the sample matrix varies.
Because of the differences between various makes and models of satisfactory instruments,
no detailed instrumental operating instructions can be provided. Instead, the analyst is referred to
the instructions provided by the manufacturer of the particular instrument.
D.1.1 Summary of Method
The method describes a technique for the simultaneous or sequential multielement
determination of trace elements in solution. The basis of the method is the measurement of atomic
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transported by an argon carrier stream to an ICP, which is produced by a radio frequency (RF)
generator. In the plasma (which is at a temperature of 6,000 to 10,000 *K), the analytes in the
aerosol are atomized, ionized, and ionic emission spectra is produced. The spectra from all analytes
are dispersed by a grating spectrometer and the intensities of the lines are monitored by
photomultiplier tubes. The photocurrents from the photomultiplier tubes are processed by a
computer system. The signal is proportional to the analyte concentration and is calibrated by
analyzing a series of standards (U.S. Environmental Protection Agency [EPA], 1983; Fassel, 1982).
A background correction technique is required to compensate for variable background
contribution to the determination of trace elements. Background should be measured adjacent to
analyte lines during sample analysis. The position selected for the background intensity
measurement, on either or both sides of the analytical line, is determined by the complexity of the
spectrum adjacent to the analyte line. The position used should be free of spectral interference and
should reflect the same change in background intensity as occurs at the analyte wavelength
measured. Generally, each instrument has different background handling capabilities. The
instrument operating manual should be consulted for guidance.
The possibility of additional interferences should also be recognized, and appropriate
corrections should be made.
D.1.2 Definitions
1. Dissolved - Those elements which will pass through a 0.45-^m membrane filter.
2. Suspended - Those elements which are retained by a 0.45-jum membrane filter.
3. Total - The concentration determined on an unfiltered sample following vigorous digestion,
or the sum of the dissolved plus suspended concentrations.
4. Total recoverable - The concentration determined on an unfiltered sample following
treatment with hot, dilute mineral acid.
5. Instrumental detection limit - The concentration equivalent to a signal due to the analyte
and which is equal to three times the standard deviation of a series of ten replicate
measurements of a reagent blank signal at the same wavelength.
6. Sensitivity - The slope of the analytical curve (i.e., functional relationship between emission
intensity and concentration).
7. Instrument check standard - A multielement standard of known concentration prepared by
the analyst to monitor and verify instrument performance on a daily basis.
8. Interference check sample - A solution containing both interfering and analyte elements
of known concentration that can be used to verify background and interelement correction
factors.
9. Quality control sample - A solution obtained from an outside source having known
concentration values; used to verify the calibration standards.
10. Calibration standards - A series of known standard solutions used by the analyst for
calibration of the instrument (i.e., preparation of the analytical curve).
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JO. Calibration standards -- A series of known standard solutions used by the analyst for
calibration of the instrument (i.e., preparation of the analytical curve).
11. Linear dynamic range -- The concentration range over which the analytical curve remains
linear.
12. Reagent blank - A volume of deionized, distilled water containing the same acid matrix as
the calibration standards carried through the entire analytical scheme.
13. Calibration blank - A volume of deionized, distilled water acidified with HNO3 and HCI.
14. Method of standard additions -- The standard additions technique involves the use of the
unknown and the unknown plus a known amount of standard.
D. 1.3 Interferences
The following types of interference effects may contribute to inaccuracies in the determination
of trace elements:
1. Spectral Interferences-Spectral interferences can be categorized as (a) overlap of a
spectral line from another element, (b) unresolved overlap of molecular band spectra, (c)
background contribution from continuous or recombination phenomena, and (d) background
contribution from stray light from the line emission of high-concentration elements. The
first of these effects can be compensated by utilizing a computer correction of the raw
data which requires the monitoring and measurement of the interfering element. The
second effect may require selection of an alternate wavelength. The third and fourth
effects can usually be compensated by a background correction adjacent to the analyte
line. In addition, users of simultaneous multielement instrumentation should assume the
responsibility of verifying the absence of spectral interference from an element that could
occur in a sample but for which there is no channel in the instrument array. Table D-2 lists
some interference effects for the recommended wavelengths given in Table D-1. The
interference information is expressed as analyte concentration equivalents (i.e., false
analyte concentrations) arising from 100 mg/L of the interfering element. The values in the
table are only approximate and should be used as a guide for determining potential
interferences. Actual values should be determined for each analytical system when
necessary.
Table D-2. Analyte Concentration Equivalent* (mg/L.) Arising from Interferences at the 100-mg/L Level
Interference
Analyte
Aluminum
Calcium
Iron
Magnesium
Silicon
Sodium
Wavelength
(nm)
308.215
317.933
259.940
279.079
288.158
588.995
At Ca
0.02
Cr
0.11
0.07
Cu
0.08
Fe
0.13
Mg
0.01
Mn
0.21
0.01
0.12
0.25
Ni
0.04
Ti
0.07
0.08
V
0.03
0.12
0.01
0.03
The wavelengths listed are recommended because of their sensitivity and overall acceptance. Other wavelengths may
be be sustituted if they can provide the needed sensitivity and are treated with the same corrective techniques for
spectral interference.
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Only those interferents listed were investigated. The blank spaces in Table D-2 indicate that
measurable interferences were not observed for the interferant concentrations listed in Table
0-3. Generally, interferences were discernible if they produced peaks or background shifts
corresponding to 2 to 5 percent of the peaks generated by the analyte concentrations (also
listed in Table D-3).
2. Physical Interferences-Physical interferences generally are considered to be effects
associated with the sample nebulization and transport processes. Changes in viscosity and
surface tension can cause significant inaccuracies, especially in samples that contain high
dissolved solids or acid concentrations. The use of a peristaltic pump may lessen these
interferences. If these types of interferences are operative, they can be reduced by dilution
of the sample or utilization of standard additions techniques.
High dissolved solids may also cause salt buildup at the tip of the nebulizer. This affects
aerosol flow rate, causing instrumental drift. Wetting the argon prior to nebulization, using
a tip washer, or diluting the sample can be used to control this problem. Better control of
the argon flow rate improves instrument performance. This is accomplished with the use of
mass flow controllers.
Table D-3. Interferant and Analyte Elemental Concentrations Used for Interference Measurements In Table D-2
Analytes
Concentration (mg/L)
Interferents
Concentration (mg/L)
Al
Ca
Fe
Mg
Na
Si
10
1
1
1
10
1
Al
Ca
Cr
Cu
Fe
Mg
Nn
Ni
Ti
V
1,000
1.000
200
200
1,000
1,000
200
200
200
200
3. Chemical Interferences-Chemical interferences are characterized by molecular compound
formation, ionization effects, and solute vaporization effects. Normally these effects are
negligible with the ICP technique. If observed, they can be minimized by careful selection
of operating conditions (i.e., incident power, observation position), by buffering of the
sample, matrix matching, and standard addition procedures. These types of interferences
can be dependent on matrix type and the specific analyte element.
D.1.4 Interference Tests
Whenever a new or unusual sample matrix is encountered, a series of tests should be
performed prior to reporting concentration data for analyte elements. These tests, outlined below,
ensure that neither positive nor negative interference effects are operative on any of the analyte
elements, thereby distorting the accuracy of the reported values.
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1. Serial Dilution-If the analyte concentration is sufficiently high (minimally a factor of 10
above the instrumental detection limit after dilution), an analysis of a dilution should agree
within 5 percent of the original determination (or within some acceptable control limit that
has been established for that matrix). If it does not, a chemical or physical interference
effect should be suspected.
2. Spiked Addition-The recovery of a spiked addition added at a minimum level of 10 x the
instrumental detection limit (maximum 100x) to the original determination should be
recovered to within 90 to 110 percent or within the established control limit for that matrix
If not, a matrix effect should be suspected. The use of a standard additions analysis
procedure can usually compensate for this effect.
Caution: The standard addition technique does not detect coincidental spectral overlap.
If overlap is suspected, use of computerized compensation, an alternate
wavelength, or comparison with an alternate method is recommended.
3. Comparison with alternate method of analysis-When investigating a new sample matrix,
a comparison test may be performed with other analytical techniques, such as atomic
absorption spectrometry or other approved methodology.
4. Wavelength scanning of analyte line region-If the appropriate equipment is available,
wavelength scanning can be performed to detect potential spectral interferences.
D.1.5 Safety
The toxicity or carcinogenicity of each reagent used in this method has not been defined
precisely. Each chemical compound should be treated as a potential health hazard. From this view-
point, exposure to these chemicals should be reduced to the lowest possible level by whatever
means available. The laboratory is responsible for maintaining a current awareness file of
Occupational Safety and Health Administration (OSHA) regulations regarding the safe handling of
the chemicals specified in this method. A reference file of material data safety sheets should also
be made available to all personnel involved in the chemical analysis. Additional references to
laboratory safety are available and have been identified (Department of Health, Education, and
Welfare [DHEW], 1977; OSHA, 1976; American Chemical Society [ACS], 1979) for the information of
the analyst.
D.2 Sample Collection, Preservation, and Storage
For the determination of trace elements, contamination and loss are of prime concern. Dust
in the laboratory environment, impurities in reagents, and impurities on laboratory apparatus which
the sample contacts are all sources of potential contamination. Sample containers can introduce
either positive or negative errors in the measurement of trace elements by (a) contributing
contaminants through leaching or surface desorption and (b) by depleting concentrations through
adsorption. Thus the collection and treatment of the sample prior to analysis requires particular
attention. Laboratory glassware including the sample bottle (whether polyethylene, polypropylene
or FEP-fluorocarbon) should be thoroughly washed with detergent and tap water; rinsed with (1:1)
nitric acid, tap water, (1:1) hydrochloric acid, tap water, and finally deionized, distilled water (in that
order).
NOTE 1: Chromic acid may be useful to remove organic deposits from glassware; however,
the analyst should be cautioned that the glassware must be thoroughly rinsed with
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water to remove the last traces of chromium. Chromic acid should not be used with
plastic bottles.
NOTE 2: If it can be documented through an active analytical quality control program using
spiked samples and reagent blanks that certain steps in the cleaning procedure are
not required for routine samples, those steps may be eliminated from the procedure.
Before collection of the sample, a decision must be made as to the type of data desired (i.e.,
dissolved, suspended, or total) so that the appropriate preservation and pretreatment steps may
be accomplished. Filtration, acid preservation, etc., are to be performed at the time the sample is
collected or as soon as possible thereafter.
For the determination of dissolved elements, the sample must be filtered through a 0.45-//m
membrane filter as soon as practical after collection. (Glass or plastic filtering apparatus are
recommended to avoid possible contamination.) Use the first 50 to 100 ml to rinse the filter flask.
Discard this portion and collect the required volume of filtrate. Acidify the filtrate with (1:1) HNO3 to
a pH of 2 or less. Normally, 3 mL of (1:1) acid per liter should be sufficient to preserve a sample.
For the determination of suspended elements, a measured volume of unpreserved sample
must be filtered through a 0.45-pm membrane filter as soon as practical after collection. The filter
plus suspended material should be transferred to a suitable container for storage and shipment.
No preservative is required.
For the determination of total or total recoverable elements, the sample is acidified with (1:1)
HNO3 to pH 2 or less as soon as possible, preferably at the time of collection. The sample is not
filtered before processing.
D.3 Equipment and Supplies
D.3.1 Inductively Coupled Plasma Atomic Emission Spectrometer
1. Computer-controlled atomic emission spectrometer with background correction.
2. Radio frequency generator.
3. Argon gas supply, welding grade or better.
D.3.2 Reagents
Acids used in the preparation of standards and for sample processing must be ultra-high
purity spectroscopic grade or equivalent. Redistilled acids are acceptable.
Standard stock solutions may be purchased or prepared from ultra-high purity grade chemicals
or metals. All salts must be dried for 1 hour at 105 *C unless otherwise specified. Typical stock
solution preparation procedures for the elements typically analyzed in soil samples are described
in steps 7 through 12, below. A mixed calibration standard solution may be prepared by combining
appropriate volumes of the stock solutions in volumetric flasks. Add 2 mL of (1:1) HNO3 and 10 mL
of (1:1) HCI and dilute to 100 mL with deionized, distilled water. Prior to preparing the mixed
standards, each stock solution should be analyzed separately to determine possible spectral
interference or the presence of impurities. Care should be taken when preparing the mixed
standards that the elements are compatible and stable. Transfer the mixed standard solutions to
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a FEP-fluorocarbon or unused polyethylene bottle for storage. Freshly mixed standards should be
prepared as needed with the realization that concentration can change due to aging. Calibration
standards must be verified initial! ,• by using a quality control sample and should be monitored
weekly for stability.
Caution: Many metal salts are extremely toxic and may be fatal if swallowed. Wash hands
thoroughly after handling.
In addition to the calibration standards, blank samples, an instrument check standard, an
interference check sample, and a quality control sample are also required for the analyses. Blanks
are described in steps 13 and 14; the remaining quality control samples are described in steps 15
through 17.
1. Acetic acid, concentrated (sp. gr. 1.06).
2. Hydrochloric acid, concentrated (sp. gr. 1.19).
3. Hydrochloric acid, (1:1)--Add 500 ml concentrated HCI (sp. gr. 1.19) to 400 ml_ deionized,
distilled water and dilute to 1 liter.
4. Nitric acid, concentrated (sp. gr. 1.41).
5. Nitric acid, (1:1)-Add 500 ml concentrated HNO3 (sp. gr. 1.41) to 400 mL deionized, distilled
water and dilute to 1 liter.
6. Deionized, distilled water-Prepare by passing distilled water through a mixed bed of cation
and anion exchange resins. Use deionized, distilled water for the preparation of all
reagents, calibration standards, and as dilution water. The purity of this water must be
equivalent to American Society for Testing and Materials (ASTM) Type II reagent water of
Specification D-1193-77 (ASTM 1984).
7. Aluminum solution, stock, 1 mL = 100 fjg AI3+--Dissolve 0.100 g of aluminum metal in an
acid mixture of 4 mL of (1:1) HCI and 1 mL of concentrated HNO3 in a beaker. Warm gently
to effect solution. When solution is complete, transfer quantitatively to a 1-L volumetric
flask, add an additional 10 mL of (1:1) HCI, and dilute to 1000 mL with deionized, distilled
water.
8. Calcium solution, stock, 1 mL = 100 pg Ca2+-Suspend 0.2498 g CaCO3, dried at 180 *C for
1 hour before weighing, in deionized, distilled water and dissolve cautiously with a minimum
amount of (1:1) HNO3. Add 10.0 mL concentrated HNO3 and dilute to 1000 mL with
deionized, distilled water.
9. Iron solution, stock, 1 mL = 100 pg Fe3+--Dissolve 0.1430 g Fe2O3 in a warm mixture of 20
mL (1:1) HCI and 2 mL of concentrated HNO3. Cool, add an additional 5 mL of concentrated
HN03, and dilute to 1000 mL with deionized, distilled water.
10. Magnesium solution, stock, 1 mL = 100 pg Mg2+--Dissolve 0.1658 g MgO in a minimum
amount of (1:1) HNO3. Add 10.0 mL concentrated HNO3 and dilute to 1000 mL with
deionized, distilled water.
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11. Silica solution, stock, 1 ml = 100 pg SiO2--Do not dry. Dissolve 0.4730 g Na2SiO3-9H2O in
deionized, distilled water. Add 10.0 mL concentrated HNO3 and dilute to 1000 ml_ with
deionized, distilled water.
12. Sodium solution, stock. 1 mL = 100 fjg Na+-Dissolve 0.2542 g NaCI in deionized, distilled
water. Add 10.0 mL concentrated HNO3 and dilute to 1000 mL with deionized, distilled
water.
13. Calibration blanks-Dilute 2 mL of (1:1) HNO3 and 10 mL of (1:1) HCI to 100 mL with
deionized, distilled water. Prepare a sufficient quantity to be used to flush the system
between standards and samples.
14. Reagent blanks-Reagent blanks contain all the reagents in the same volumes as used in
the processing of the samples. The reagent blank should be carried through the complete
procedure and should contain the same acid concentration in the final solution as in the
sample solution used for analysis.
15. Instrument check standard-Combine compatible elements at a concentration equivalent
to the midpoint of their respective calibration curves.
16. Interference check sample-Select a representative sample which contains minimal
concentrations of the analytes of interest but a known concentration of interfering elements
that will provide an adequate test of the correction factors. Spike the sample with the
elements of interest at the approximate concentration of either 100 pg/L or 5 times the
estimated detection limits given in Table D-1. (For effluent samples of expected high
concentrations, spike at an appropriate level.) If the type of samples analyzed is varied,
a synthetically prepared sample may be used as long as the above criteria and intent are
met.
17. Quality control sample-Prepare a solution in the same acid matrix as the calibration
standards at a concentration near 1 mg/L.
D.4 Preparation
D.4.1 Sample Preparation
For the determinations of dissolved elements, the filtered, preserved sample may often be
analyzed as received. The acid matrix and concentration of the samples and calibration standards
must be the same. If a precipitate has formed upon acidification of the sample or during transit
or storage, it must be redissolved before the analysis by adding additional acid or by heat, or both.
For the determination of suspended elements, transfer the membrane filter containing the
insoluble material to a 150-mL Griffin beaker and add 4 mL concentrated HN03. Cover the beaker
with a watch glass and heat gently. The warm acid will soon dissolve the membrane. Increase the
temperature of the hot plate and digest the material. When the acid has nearly evaporated, cool
the beaker and watch glass and add another 3 mL of concentrated HNO3. Cover and continue
heating until the digestion is complete; digestion is generally indicated by a light colored digest ate.
Evaporate to near dryness (2 mL), cool, add 10 mL HCI (1:1) and 15 mL deionized, distilled water per
100 mL dilution, and warm the beaker gently for 15 minutes to dissolve any precipitate or residue.
Allow to cool, wash down the watch glass and beaker walls with deionized distilled water, and filter
the sample to remove any insoluble material that could clog the nebulizer. Adjust the volume based
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on the expected concentrations of elements present. This volume will vary depending on the
elements to be determined. The sample is now ready for analysis. Concentrations so determined
shall be reported as "suspended."
NOTE: In place of filtering, and after diluting and mixing, the sample may be centrifuged or
allowed to settle by gravity overnight to remove insoluble material.
For the determination of total elements, choose a measured volume of the well mixed, acid-
preserved sample appropriate for the expected level of elements and transfer it to a Griffin beaker.
Add 3 ml of concentrated HN03. Place the beaker on a hot plate and evaporate to near dryness
cautiously, making certain that the sample does not boil and that no area on the bottom of the
beaker is allowed to go dry. Cool the beaker and add another 5 ml portion of concentrated HNO3.
Cover the beaker with a watch glass and return it to the hot plate. Increase the temperature of the
hot plate so that a gentle reflux action occurs. Continue heating, adding additional acid as neces-
sary, until the digestion is complete (generally indicated when the digestate is light in color or does
not change in appearance with continued refluxing.) Again, evaporate to near dryness and cool the
beaker. Add 10 ml of (1:1) HCI and 15 ml of deionized, distilled water per 100 ml of final solution
and warm the beaker gently for 15 minutes to dissolve any precipitate or residue resulting from
evaporation. Allow to cool; wash down the beaker walls and watch glass with deionized, distilled
water and filter the sample to remove insoluble material that could clog the nebulizer. Adjust the
sample to a predetermined volume based on the expected concentrations of elements present. The
sample is now ready for analysis. Concentrations so determined shall be reported as "total."
NOTE: If the sample analysis solution has a different acid concentration from that given
below, but does not introduce a physical interference or affect the analytical result, the
same calibration standards may be used.
For the determination of total recoverable elements, choose a measured volume of a well
mixed, acid-preserved sample appropriate for the expected level of elements and transfer it to a
Griffin beaker. Add 2 ml of (1:1) HN03 and 10 ml of (1:1) HCI to the sample and heat on a steam
bath or hot plate until the volume has been reduced to near 25 mL, making certain the sample does
not boil. After this treatment, cool the sample and filter to remove insoluble material that could clog
the nebulizer. Adjust the volume to 100 mL and mix. The sample is now ready for analysis.
Concentrations so determined shall be reported as "total."
D.4.2 Calibration and Standardization
Prepare and calibrate blank standards and a series of dilute calibration standards from the
stock solution spanning the expected sample concentration range. Match the acid content of the
standards to that of the samples. A multielement standard may be prepared.
D.4.3 Operating Conditions
Because of the differences between various makes and models of satisfactory instruments,
no detailed operating instructions can be provided. Instead, the analyst should follow the
instructions provided by the manufacturer of the particular instrument. Sensitivity, instrumental
detection limit, precision, linear dynamic range, and interference effects must be investigated and
established for each individual analyte line on that particular instrument. It is the responsibility of
the analyst to verify that the instrument configuration and operating conditions satisfy the analytical
requirements, and to maintain quality control data confirming instrument performance and analytical
results.
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D.5 Quality Assurance and Quality Control
D.5.1 Instrument Quality Control Checks
Check the instrument standardization by analyzing appropriate quality control check standards
as indicated below:
1. Analyze an appropriate instrument check standard containing the elements of interest at
a frequency of 10 percent. This check standard is used to determine instrumental drift. If
agreement is not within 5 percent of the expected values or within the established control
limits, whichever is lower, the analysis is out of control. The analysis should be terminated,
the problem corrected, and the instrument recalibrated. Analyze the calibration blank at a
frequency of 10 percent. The result should be within the established control limits of 2
standard deviations of the mean value. If not, repeat the analysis two more times and
average the three results. If the average is not within the control limit, terminate the
analysis, correct the problem, and recalibrate the instrument,
2. To verify interelement and background correction factors, analyze the interference check
sample at the beginning, end, and at periodic intervals throughout the sample run. Results
should fall within the established control limits of 1.5 times the standard deviation of the
mean value. If not, terminate the analysis, correct the problem, and recalibrate the
instrument.
3. A quality control sample obtained from an outside source must first be used for the initial
verification of the calibration standards. A fresh dilution of this sample must be analyzed
every week thereafter to monitor the instrument stability. If the results are not within ±5
percent of the true value listed for the control sample, prepare a new calibration standard
and recalibrate the instrument. If this does not correct the problem, prepare a new stock
standard and a new calibration standard and repeat the calibration.
D.5.2 Precision and Accuracy
In an EPA round-robin phase 1 study, seven laboratories applied the ICP technique to acid-
distilled water matrices that had been dosed with various metal concentrates. Table 0-4 lists the
true value, the mean reported value, and the mean percent relative standard deviation.
Table D-4. Inductively Coupled Plasma Emission Spectroscopy Precision and Accuracy Data"
Sample 1 Sample 2 Sample 3
Element
Al
Fe
Trua
Value
0/g/L)
700
600
Mean
Reported
Value
(pg/L)
696
594
Mean
%RSDb
5.6
3.0
True
Value
(pg/U
60
20
Mean
Reported
Value
(P9/L)
62
19
Mean
%RSD
33
15
True
Value
(MJ/U
160
180
Mean
Reported
Value
teJ/L)
161
178
Mean
%RSD
13.0
6.0
* Not all elements were analyzed by all laboratories. Ca and Mg were not determined.
%RSD = percent relative standard deviation.
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D.6 Procedure
1. Set up instrument with proper operating parameters as established in Section D.4.3. The
instrument must be allowed to become thermally stable before analysis begins. This
usually requires at least 30 minutes of operation prior to calibration.
2. Initiate appropriate operating configuration of computer.
3. Profile and calibrate instrument according to recommended procedures described in Section
D.4.2, using the typical mixed calibration standard solutions described in Section D.3.2.
Flush the system with the calibration blank between each standard. (The use of the
average intensity of multiple exposures for both standardization and sample analysis has
been found to reduce random error.)
4. Before beginning the sample run, reanalyze the highest mixed calibration standard as if it
were a sample. Concentration values obtained should not deviate from the actual values
by more than ±5 percent (or the established control limits, whichever is lower). If they do,
follow the recommendations of the instrument manufacturer to correct for this condition.
5. Begin the sample run, flushing the system with the calibration blank solution between each
sample. Analyze the instrument check standard and the calibration blank after each 10
samples.
6. If it has been found that methods of standard additions are required, the following
procedure is recommended:
The standard additions technique involves preparing new standards in the sample matrix
by adding known amounts of standard to one or more aliquots of the processed sample
solution. This technique compensates for a sample constituent that enhances or
depresses the analyte signal and thus produces a different slope from that of the
calibration standards. It will not correct for additive interference which causes a
baseline shift. The simplest version of this technique is the single-addition method. The
procedure is as follows. Two identical aliquots of the sample solution, each of volume
Vx> are taken. To the first (labeled A) is added a small volume V. of a standard analyte
solution of concentration c8. To the second (labeled B) is added the same volume V. of
the solvent. The analytical signals of A and B are measured and corrected for
nonanalyte signals. The unknown sample concentration cx is calculated:
SBVscs
c, =
Where SA and SB are the analytical signals (corrected for the blank) of solutions A and
B, respectively. V, and c. should be chosen so that SA is roughly twice SB on the
average. It is best if V, is made much less than Vx, and thus c, is much greater than
cx. If a concentration step is used, the additions are best made first and carried through
the entire procedure. For the results from this technique to be valid, the following
limitations must be taken into consideration:
a. The analytical curve must be linear.
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b. The chemical form of the analyte added must respond in the same manner as the
analyte in the sample.
c. The interference effect must be constant over the working range of concern.
d. The signal must be corrected for any additive interference.
D.7 Calculations
Generally, instruments are calibrated to output sample results directly in concentration units.
If not, then a manual calibration curve should be prepared and sample concentrations determined
by comparing the sample signal to the calibrated curve. If dilutions were performed, the appropriate
factor should be applied to sample values. Report results as mg/L for each analyte.
D.8 References
American Chemical Society. 1979. Safety in Academic Laboratories, 3rd ed. Committee on Chemical
Safety, ACS, Washington, O.C.
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specification for Reagent Water, D-1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
Department of Health, Education, and Welfare. 1977. Carcinogens - Working with Carcinogens. No.
77-206. DHEW, Public Health Service, Center for Disease Control, National Institute for
Occupational Safety and Health, Cincinnati, Ohio.
Fassel, V. A. 1982. Analytical Spectroscopy with Inductively Coupled Plasma • Present Status and
Future Prospects. In: Recent Advances in Analytical Spectroscopy. Pergamon Press, Oxford
and New York.
Occupational Safety and Health Administration. 1976. OSHA Safety and Health Standards, General
Industry. OSHA 2206 (29 CFR 1910). OSHA, Washington, D.C.
U.S. Environmental Protection Agency. 1983 (revised). Methods for Chemical Analysis of Water and
Wastes. EPA-600/4-79-020. U.S. Environmental Protection Agency, Cincinnati, Ohio.
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Appendix E
Emission Spectroscopic Methods
(Adapted from Methods 324B and 322B in Standard Methods for the
Examination of Water and Wastewater [APHA, 1985])
E.1 Overview
When analyzing by emission spectroscopy (ES), the better instruments can be used to
determine sodium levels approximating 100 //g/L With proper modifications in technique, the range
of sodium measurement can be extended to 10 /ug/L or lower. Potassium levels of approximately
0.1 mg/L can also be determined.
E.1.1 Summary of Method
Trace amounts of sodium and potassium are determined by ES at wavelengths of 589 and
766.5 nm, respectively. The sample is sprayed into a gas flame, and excitation is carried out under
carefully controlled and reproducible conditions. The desired spectral line is isolated by the use of
interference filters or by a suitable slit arrangement in light dispersing devices such as prisms or
gratings. The intensity of light is measured by a phototube potentiometer or other appropriate
circuit. The intensity of light at the appropriate wavelength (e.g., 589 nm for Na+) is approximately
proportional to the concentration of the element. If alignment of the wavelength dial with the prism
is not precise in the available photometer, the exact wavelength setting can be determined from the
maximum needle deflection and can then be used for the emission measurements. The calibration
curve may be linear, but has a tendency to level off at higher concentrations.
E1.2 Interferences
Emission spectrometers operating on the internal standard principle may require adding a
standard lithium solution to each working standard and sample. The optimum lithium concentration
may vary among individual instruments; minimize interference by the following:
1. Operate in the lowest practical range.
2. Add radiation buffers to suppress ionization and anion interference. Among common
anions capable of causing radiation interference are CI", SO/", and HCO3" in relatively large
amounts.
3. Introduce identical amounts of the same interfering substances present in the sample into
the calibration standards.
4. Prepare a family of calibration curves encompassing incremental concentrations of a
common interferant.
5. Apply an experimentally determined correction in those instances where the sample
contains a single important interference.
6. Remove interfering ions.
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7. Remove burner clogging particulate matter from the sample by filtering through a
quantitative filter paper of medium retentiveness.
8. Incorporate a nonionic detergent in the standard lithium solution to assure proper aspirator
function.
9. Use the standard additions technique. The standard additions approach is described in
Section C.4. Its use involves adding an identical portion of sample to each standard and
determining the sample concentration by mathematical or graphical evaluation of the
calibration data.
10. Use the internal standard technique. Potassium and calcium interfere with sodium
determination by the internal-standard method if the potassium-to-sodium ratio is 2:5:1 and
the calcium-to-sodium ratio is >10:1. Sodium and calcium may interfere with potassium
determination by the internal standard method if the sodium-to-potassium ratio is ^5:1 or
the calcium-to-potassium ratio is >10:1. Magnesium interference does not appear until the
magnesium-to-sodium ratio or magnesium-to-potassium ratio exceeds 100 percent.
E.1.3 Safety
Wear protective clothing (laboratory coat and gloves) and safety glasses when preparing
reagents, especially when concentrated acids and bases are used. The use of concentrated acids
should be restricted to a fume hood. Many metal salts are extremely toxic and may be fatal if
swallowed. Wash hands thoroughly after handling.
Follow the safety precautions of the manufacturer when operating instruments. Gas cylinders
should always be chained or bolted in an upright position.
E.2 Sample Collection, Preservation, and Storage
For the determination of trace elements, contamination and loss are of prime concern. Dust
in the laboratory environment, impurities in reagents, and impurities on laboratory apparatus which
the sample contacts are all sources of potential contamination. Sample containers can introduce
either positive or negative errors in the measurement of trace elements by (a) contributing
contaminants through leaching or surface desorption and (b) by depleting concentrations through
adsorption. Thus the collection and treatment of the sample prior to analysis requires particular
attention. Laboratory glassware including the sample bottle (whether polyethylene, polypropylene
or FEP-fluorocarbon) should be thoroughly washed with detergent and tap water; rinsed with (1:1)
nitric acid, tap water, (1:1) hydrochloric acid, tap water and finally deionized, distilled water (in that
order).
E.3 Equipment and Supplies
E.3.1 Equipment Specifications
1. Emission spectrometer, direct-reading or internal-standard type; or an atomic absorption
spectrometer operated in the flame emission mode.
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E.3.2 Reagents
NOTE 1: Rinse all glassware with 1:15 HNO3 followed by several portions of DI water.
NOTE 2: To minimize sodium or potassium pickup, store all solutions in plastic bottles. Use
small containers to reduce the amount of dry element that may be picked up from the
bottle walls when the solution is poured. Shake each container thoroughly to wash
accumulated salts from walls before pouring solution.
1. Standard lithium solution-Use either LiCI or LiNO3 to prepare standard lithium solution
containing 1.00 mg Li/1.00 ml.
a. Dry LiCI overnight in an oven at 105 °C. Weigh rapidly 6.109 g, dissolve in water, and
dilute to 1,000 mL.
b. Dry LiNO3 overnight in an oven at 105 °C. Weigh rapidly 9.935 g, dissolve in water, and
dilute to 1,000 mL
Prepare a new calibration curve whenever the standard lithium solution is changed. Where
circumstances warrant, alternatively prepare a standard lithium solution containing 2.00 mg
or even 5.00 mg Li/1.00 mL.
2. Stock sodium solution-Dissolve 2.542 g NaCI dried at 140 °C and dilute to 1000 mL with
water; 1.00 mL = mg Na+.
3. Intermediate sodium solution-Dilute 10.00 mL stock sodium solution with water to 100.0
mL; 1.00 mL = 100 /KJ Na4. Use this intermediate solution to prepare calibration curve in
sodium range of 1 to 10 mg/L.
4. Standard sodium solution-Dilute 10.00 mL intermediate sodium solution with water to 100
mL; 1.00 mL = 10.0 /jg Na+. Use this solution to prepare calibration curve in sodium range
of 0.1 to 1.0 mg/L.
5. Stock potassium solution-Dissolve 1.907 g KCI dried at 110 °C and dilute to 1000 mL with
water; 1 mL = 1.00 mg K+.
6. Intermediate potassium solution-Dilute 10.0 mL stock potassium solution with water to 100
mL; 1.00 mL = 0.100 mg K+. Use this solution to prepare calibration curve in potassium
range of 1 to 10 mg/L.
7. Standard potassium solution-Dilute 10.0 mL intermediate potassium solution with water
to 100 mL; 1.00 mL = 0.010 mg K+. Use this solution to prepare calibration curve in
potassium range of 0.1 to 1.0 mg/L.
8. Water-Water used in all preparations should conform to ASTM specifications for Type I
reagent grade water (ASTM, 1984).
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E.4 Calibration and Standardization
NOTE: Locate instrument in an area away from direct sunlight or constant light emitted by an
overhead fixture and free of drafts, dust, and tobacco smoke. Guard against contamination
from corks, filter paper, perspiration, soap, cleansers, cleaning mixtures, and inadequately
rinsed apparatus.
Because of differences between makes and models of instruments, it is impossible to
formulate detailed operating instructions. Follow manufacturer's recommendations for selecting
proper photocell and wavelength, adjusting slit width and sensitivity, appropriate fuel and air or
oxygen pressures, and the steps for warm-up, correcting for interferences and flame background,
rinsing of burner, igniting sample, and measuring emission intensity.
Prepare a blank and sodium or potassium calibration standards in stepped amounts in any
of the following applicable ranges: 0 to 1.0, 0 to 10, or 0 to 100 mg/L Starting with the highest
calibration standard and working toward the most dilute, measure emission at 589 nm for sodium
and 766 nm for potassium. Repeat the operation with both calibration standards and samples
enough times to secure a reliable average reading for each solution. Construct a calibration curve
from the calibration standards.
E.5 Quality Control
Quality control (QC) is an integral part of any measurement procedure in order to ensure that
results are reliable. A summary of internal QC procedures for each method is given in Table 3-1 and
copies of all QC forms are provided in Appendix B. Details on internal QC procedures used in the
DDRP are described below.
E.6 Procedure
1. Calibrate the instrument.
2. Analyze samples.
3. Determine concentration of sample from the calibration curve. Where a large number of
samples must be run routinely, the calibration curve provides sufficient accuracy. If greater
precision and accuracy are desired and time is available, use the bracketing approach
described below.
4. Bracketing approach-From the calibration curve, select and prepare standards that
immediately bracket the emission intensity of the sample. Determine emission intensities
of the bracketing standards (one standard slightly less and the other slightly greater than
the sample) and the sample as nearly simultaneously as possible. Repeat the
determination on bracketing standards and sample. Calculate the concentration by the
equation in Section E.7 and average the findings.
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E.7 Calculations
For direct reference to the calibration curve:
mg Na+ (or K+)/L = (mg Na+ (or K+)/L in portion) x D
For the bracketing approach:
mg Na+ (or K+)/L = {[(B - A) (s - a) + (b - a)] + A} x D
where:
B = mg Na+ (or K+)/L in upper bracketing standard,
A = mg Na+ (or K+)/L in lower bracketing standard,
b = emission intensity of upper bracketing standard,
a = emission intensity of lower bracketing standard,
s = emission intensity of sample, and
_ , mL sample + mL PI water
D = dilution ratio = mL sample
E.8 References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specification for Reagent Water, D-1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
6U.S. GOVERNMENT PRINTING OFFICE: 1 9 9 0 .7 5 1 .8 I o/
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