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ERDC/CRREL TR-11-15 Guidance for Soil Sampling of Energetics and Metals Cold Regions Research and Engineering Laboratory Susan Taylor, Thomas F. Jenkins, Susan Bigl, Alan D. Hewitt, Marianne E. Walsh and Michael R. Walsh October 2011 Approved for public release; distribution is unlimited. DEDICATION: We dedicate this report to our late colleague Alan Hewitt. He worked tirelessly to develop sampling methods and protocols for evaluating energetic residues on military training ranges. He also passionately shared what he had learned with audiences large and small. This document would not have been possible without his research contributions. We miss you Alan. ERDC/CRREL TR-11-15 October 2011 Guidance for Soil Sampling of Energetics and Metals Susan Taylor, Thomas F. Jenkins, Susan Bigl, Alan D. Hewitt, Marianne E. Walsh and Michael R. Walsh Cold regions Research and Engineering Laboratory U.S. Army Engineer Research and Development Center 72 Lyme Road Hanover, NH 03755 Final report Approved for public release; distribution is unlimited. Prepared for U.S. Army Environmental Command ERDC/CRREL TR-11-15 ii Abstract: Information is presented on how to collect and process soil samples to quantify ex-plosives, propellants and metals from training range soils. This document outlines how to esti-mate the average concentration of energetic compounds and metals in soils and determine the error in the estimated concentration. DISCLAIMER: The contents of this report are not to be used for advertising, publication, or promotional purposes. Citation of trade names does not constitute an official endorsement or approval of the use of such commercial products. All product names and trademarks cited are the property of their respective owners. The findings of this report are not to be construed as an official Department of the Army position unless so designated by other authorized documents. DESTROY THIS REPORT WHEN NO LONGER NEEDED. DO NOT RETURN IT TO THE ORIGINATOR. ERDC/CRREL TR-11

LIBRARY OCT ! 2 1999 Bureau of Reclamation Reclamation Service Center US Army Corps of Engineers® Cold Regions Research & Engineering Laboratory On-Site Method for Measuring Nitroaromatic and Nitramine Explosives in Soil and Groundwater Using GC-NPD Feasibility Study Alan D. Hewitt and Thomas F. Jenkins August 1999 Abstract: An on-site method has been developed for estimating concentrations of TNT, RDX, 2,4-DNT, and the Iwo most commonly encountered environmental tran s fo rm a tio n p rodu cts of TNT, 2 -am in o -4 ,6 - dinitrotoluene and 4-amino-2,6-dinitrotoluene, in soil and groundwater using gas chromatography and the nitrogen-phosphorus detector (NPD). Soil samples (20 g) are extracted by shaking with 20 mL of acetone, and extracts are filtered through a Millex SR (0.5-pm) filter. Groundwater samples (1 L) were passed through SDB-RPS extraction disks that were subsequently ex­tracted with 5 mL of acetone. A 1 - p i volume of a soil or water extract is manually injected into a field-transport­able gas chromatograph equipped with a NPD and a heated injection port. Separations are conducted on a Restek Crossbond 100% dimethyl polysiloxane column, 6 m x 0.53-mm i.d., 1.5 mm, using nitrogen carrier gas at 9.5 mL/rnin. Retention times range from 3.0 min. for 2,4-dinitrotoluene (2,4-DNT) to 5.6 min. for 2-amino-4,6- dinitrotoluene. Method detection limits were less than 0.16 mg/kg for soil and less than 1.0 pg/L for groundwater. One of the major advantages of this method, over cur­rently available colorimetric and enzyme immunoassay on-site methods, is the ability to quantity individual target analytes that often coexist in soils and groundwater con­taminated with explosive residues. This method will be particularly useful at military antitank firing ranges where it is necessary to quantity residual concentrations of RDX in the presence of high concentrations of HMX, and when the transformation products of TNT need to be identified. How to get copies of CRREL technic

JUN 2 4 1999 Bureau of Reclamation Reclamation Sfcrvirp O ntPi US Army Corps of Engineers® Cold Regions Research & Engineering Laboratory Storage and Preservation of Soil Samples for Volatile Compound Analysis Alan D. Hewitt May 1999 Abstract: Traditionally, soil samples obtained for char­acterizing or monitoring sites for volatile organic com­pounds (VOCs) have been transported off site before ini­tiating the preparation steps necessary for analysis. In the most recent regulatory guidance, only a two-day holding period at 4 + 2°C is recommended before a sample should be preserved, so as to allow storage up to 14 days prior to Instrumental analysis. The transpor­tation and storage of soil samples were evaluated for (1) covered core barrel liners, (2) En Core samplers, and (3 ) empty volatile organic analysis (VOA) vials under different conditions. Core barrel liners cov­ered with either of Iwo formulations of Teflon sheeting or aluminum foil failed to prevent rapid losses of VOCs. En Core samplers and otherwise empty VOA vials were suitable transportation and storage chambers for samples. These chambers not only meet the initial requirement to retain VOCs for two days when held at 4 ± 2°C for transportation purposes, but fre­quently showed no significant loss of VOCs after placing in a freezer and storing at -1 2 ± 3°C for an additional 12 days. How to get copies of CRREL technical publications: Department of Defense personnel and contractors may order reports through the Defense Technical Information Center: DTIC-BR SUITE 0944 8725 JOHN J KINGMAN RD FT BELVOIRVA 22060-6218 Telephone 1 800 225 3842 E-mail help@dtic.mil msorders@dtic.mil WWW http://www.dtic.dla.mil/ All others may order reports through the National Technical Information Service: NTIS 5285 PORT ROYAL RD SPRINGFIELD VA 22161 Telephone 1 800 553 6847 or 1 703 605 6000 1 703 487 4639 (TDD for the hearing-impaired) E-mail orders@ntis.fedworld.gov WWW http://www.ntis.gov A complete list of all CRREL techni

*v!ARI 2 1998 Bureau of Recla™rp",eI Soil-Vapor Vel ^“IfcreTe Soil Sample Measurements for VOCs in the Near-Surface Vadose Zone Feasibility Study Alan D. Hewitt June 1998 Abstract: Soil vapor samples were taken from t m beneath the ground surface at 16 different locations. Measured trichloroethene (TCE) in these samples was compared to that obtained for a collocated sample of the soil matrix. The linear slope (0.806) and strong correlation (r2 = 0.950) obtained for this comparison of soil vapor (mg TCE/L) to soil mass (mg TCE/kg) concentrations are in good agreement with recent theoretical and empirical models for this volatile organic compound (VOC) in a low organic carbon soil matrix. This strong relationship suggests that active soil-vapor measurements could be used as an alternative to collecting and analyzing discrete soil samples for establishing both the presence and con­centration of VOCs during site characterization and monitoring. Moreover, the techniques and instruments described here are robust, simple to use, and de­signed to enhance the reliability of soil-gas surveys to characterize vadose zone VOC contamination. How to get copies of CRREL technical publications: Department of Defense personnel and contracfors may order reports fhrough the Defense Technical Information Center: DTIC-BR SUITE 0944 8725 JOHN J KINGMAN RD FT BELVOIRVA 22060-6218 Telephone 1 800 225 3842 E-mail help@dtic.mil msorders@dtic.mil WWW http://www.dtic.mil/ All others may order reports through the National Technical Information Service: NTIS 5285 PORT ROYAL RD SPRINGFIELD VA 22161 Telephone 1 703 487 4650 1 703 487 4639 (TDD for the hearing-impaired) E-mail orders@ntis.fedworld.gov WWW http://www.fedworld.gov/ntis/ntishome.html A complete list of all CRREL technical publications is available from USACRREL (CECRL-IB) 72 LYME RD HANOVER NH 03755-1290 Telephone 1 603 646 4338 E-mail techpubs@crrel.usace.army.mil For information on all aspects of the Cold Regions Research and Enginee

JUN 2 3 1997 Bureau of Reclamation Reclamation Service Center Preparing Soil Samples for Volatile Organic Compound Analysis Alan D, Hewitt April 1997 $ Abstract: Three equilibrium headspace and three sol­vent extraction methods of preparing soil samples for determining volatile organic compounds (VOCs) were compared. Soil samples were spiked with five gasoline range aromatic compounds and four chlorinated com­pounds using Iwo different laboratory procedures that limit volatilization and biodegradation losses. All com­parisons were made with sample triplicates of one or more soil types. Recovery efficiencies for the prepara-tion methods depended on soil organic carbon content, octanol-water partition coefficients of specific analytes, length of solvent extraction, and the spiking procedure used. In general, methanol extraction was the most robust method for recovering spiked VOCs. Recovery efficiencies for VOCs with tetraethylene glycol dimethyl ether and poly(propylene)glycol, as well as three equi­librium headspace methods, varied with the parameters tested. How to get copies of CRREL technical publications: Department of Defense personnel and contractors may order reports through the Defense Technical Information Center: DTIC-BR SUITE 0944 8725 JOHN J KINGMAN RD FT BELVOIRVA 22060-6218 Telephone 1 800 225 3842 E-mail help@dtic.mil msorders@dtic.mil WWW http://www.dtic.dla.mil/ All others may order reports through the National Technical Information Service: NTIS 5285 PORT ROYAL RD SPRINGFIELD VA 22161 Telephone 1 703 487 4650 1 703 487 4639 (TDD for the hearing-impaired) E-mail orders@ntis.fedworld.gov WWW http://www.fedworld.gov/ntis/ntishome.html A complete list of all CRREL technical publications is available from: USACRREL (CECRL-LP) 72 LYME RD HANOVER NH 03755-1290 Telephone 1 603 646 4338 E-mail techpubs@crrel.usace.army.mil For information on all aspects of the Cold Regions Research and Engineering Laboratory, visit our World Wide Web site: http://www.crrel.

JUN - 3 1997 Bureau of Reclamation Reclamation Service Center Detecting Metallic Primary Explosives with a Portable X-ray Fluorescence Spectrometer Alan D. Hewitt April 1997 Abstract: X-ray fluorescence spectrometry (XRF) analysis is a practical means of performing in-situ screening to establish the presence of high concentra­tions (>0.1% or 1000 ppm) of lead (Pb) and/or mer­cury (Hg). These two metals are of special military interest because they are constituents in three primary explosives: lead azide [Pb(N3) 2], lead styphnate (CeHOeNsPb), and mercury fulminate [Hg(CNO>2] • The success of in-situ XRF analysis to perform this task depends on instrumental sensitivity, selectivity, effec­tive sample volume, transportability, and user friend-liness. Laboratory experiments established that the MAP-3 XRF spectrum analyzer (SCITEC Corporation) is well-suited for this application. This instrument is self-contained, portable, and equipped with a Co-57 source that allows for a simultaneous analysis of both the K and L energy lines of Pb and Fig, among other metals. Laboratory experiments established that high concentrations of Pb and Hg could be detected in an active sample area of cylindrical shape, approximately 1.0 cm In diameter and 1.5 cm In depth. How to get copies of CRREL technical publications: Department of Defense personnel and contractors may order reports through the Defense Technical Information Center: DTIC-BR SUITE 0944 8725 JOHN J KINGMAN RD FT BELVOIRVA 22060-6218 Telephone 1 800 225 3842 E-mail help@dtic.mil msorders@dtlc.mil WWW http://www.dtlc.dla.mil/ All others may order reports through the National Technical Information Service: NTIS 5285 PORT ROYAL RD SPRINGFIELD VA 22161 Telephone 1 703 487 4650 1 703 487 4639 (TDD for the hearing-impaired) E-mail orders@ntls.fedworld.gov WWW http ://www.fedworld .gov/ntls/ntlshome. html A complete list of all CRREL technical publications is available from: USACRREL (CECRL-LP) 72 LYME RD HANOVER NH 03755-1290 Tele

Ti GB 2401 .C6s No.97-12 1997 Estimating the Total Concentration of Volatile Organic Compounds in Soil A Decision Tool for Sample Handling Alan D. Hewitt and Nicole J.E. Lukash April 1997 Abstract: This report describes an on-site method of estimating the total concentration of Volatile Organic Compounds (VOCs) in soil, relative to a site-specific 0.2-mg/kg standard. This decision tool allows on-site sampling activities to incorporate the appropriate soil sample collection and handling protocols required by different methods of instrumental analysis. Coupling a rapid method for estimating the total VOC concentra­tion with sampling procedures that limit substrate dis­aggregation and exposure complements efforts to achieve site-representative estimates for vadose zone contamination. How to get copies of CRREL technical publications: Department of Defense personnel and contractors may order reports through the Defense Technical Information Center: DTIC-BR SUITE 0944 8725 JOHN J KINGMAN RD FT BELVOIRVA 22060-6218 Telephone 1 800 225 3842 E-mail help@dtic.mil msorders@dtic.mil WWW http://www.dtic.dla.mil/ All others may order reports through the National Technical Information Service: NTIS 5285 PORT ROYAL RD SPRINGFIELD VA 22161 Telephone 1 703 487 4650 1 703 487 4639 (TDD for the hearing-impaired) E-mail orders@ntis.fedworld.gov WWW http://www.fedworld.gov/ntis/ntishome.html A complete list of all CRREL technical publications is available from: USACRREL (CECRL-LP) 72 LYME RD HANOVER NH 03755-1290 Telephone 1 603 646 4338 E-mail techpubs@crrel.usace.army.mil For information on all aspects of the Cold Regions Research and Engineering Laboratory, visit our World Wide Web site: http://www.crrel.usace.army.mil ¿'^'Special Report 97-12 \cffi BUREAU OF RECLAMATION DENVER LIBRARY US Army Corps of Engineers® Cold Regions Research & Engineering Laboratory Estimating the Total Concentration of Volatile Organic Compounds in Soil A Decision Tool for Sample Handling Alan D. Hewitt an

[JP P * o\ NOV Í 2 1996 Bureau of Reclamation .Reclamation Service fW o r Establishing a Relationship Between Passive Soil Vapor and Grab Sample Techniques for Determining Volatile Organic Compounds Alan D. Hewitt September 1996 Abstract: A passive soil vapor and an in-vial sample handling and analysis method were compared for esti­mating volatile organic compound (VOC) contamination in the near-surface vadose zone. These Iwo methods of VOC site characterization, although very different op­erationally, established very similar trends for trichloro­ethylene (TCE) contamination. The correlation (r2 = 0.944) of the results from these Iwo methods shows a much better agreement than what has been reported between comparisons of in-vial methods (or solvent immersion) and conventional soil sample collection and handling methods often used for site characteriza­tion activities. The strong correlation between these two methods and from grab samples taken 15 cm apart indicates that this analyte is homogeneously distrib­uted as compared to metals and semivolatile organic compounds. For contaminants such as TCE, soil vapor measurement technologies offer a promising means of estimating subsurface concentrations in locations were grab samples cannot be easily obtained. How to get copies of CRREL technical publications: Department of Defense personnel and contractors may order reports through the Defense Technical Information Center- DTIC-BR SUITE 0944 8725 JOHN J KINGMAN RD FT BELVOIRVA 22060-6218 Telephone 1 800 225 3842 E-mail help@dtlc.mil msorders@dtic.mil WWW http://www.dtic.dla.mil/ All others may order reports through the National Technical Information Service: NTIS 5285 PORT ROYAL RD SPRINGFIELD VA 22161 Telephone 1 703 487 4650 1 703 487 4639 (TDD for the hearing-impaired) E-mail orders@ntls.fedworld.gov WWW http://www.fedworld.gov/ntis/ntishome.html A complete list of all CRREL technical publications is available from: USACRREL (CECRL-TL) 72 LYME RD HANOVER NH 03755-1290

LIBRARY AUG I I 1995 Bureau of Reclamation Reclamation Service Center Rapid Screening of Metals Using Portable High-Resolution X-Ray Fluorescence Spectrometers Alan D. Hewitt April 1995 (Sk [UU] ûg Abstract Analysis of copper, zinc, arsenic, lead, chromium, cobalt, nickel, mercury, thallium, selenium, silver, antimony, cadmium, tin, and barium was performed on soils and other particle matrices using Iwo field-portable high-resolution X-ray fluorescence spectrometers (XRF). Quantitative determinations were based on fundamental parameter analysis and a second method that relies on analyte response factors and uses the Compton Ka incoherent backscatter peak for matrix normalization. These two melhods of instrumental analysis require only a few reference materials and are relatively insensitive to sample matrix composition. This study assessed the capability of these Iwo rapid XRF analysis methods by determining metal concentrations in reference materials, field samples, and laboratory spiked soils. With the exception of nickel, cobalt, and chromium, concentrations within 50% of the expected values were consistently obtained at and below 1000 ng/g. For conversion of SI units to non-SI units of measuremenf consult ASTM Standard E380-93, Standard Practice for Use of the International System o f Units, published by the American Society for Testing and Materials, 1916 Race St., Philadelphia, Pa. 19103. This report is printed on paper that contains a minimum of 50% recycled material. ?ô6 J OV J O* BUREAU OF RECLAMATION DENVER LIBRARY 'V F Special Report 95-14 4504^751 rnvii ca US Army Corps of Engineers Cold Regions Research & Engineering Laboratory Rapid Screening of Metals Using Portable High-Resolution X-Ray Fluorescence Spectrometers Alan D. Hewitt April 1995 Prepared for U.S. ARMY ENVIRONMENTAL CENTER SFIM-AEC-ET-CR-95039 Approved for public release; distribution is unlimited. 92049721 PREFACE This report was prepared by Alan D. Hewitt, Research Physical Scientist, Geol

1994 Screening for Metals by X-Ray Fluorescence Spectrometry Using a Single Calibration Standard Alan D. Hewitt July 1994 Abstract Analysis for copper, zinc, arsenic and lead was performed on a variety of solid particle matrices using a portable, high-resolution X-ray fluorescence (XRF) spectrometer. All quantitative determinations were based on an instrumental calibration method that uses a single certified reference material to establish elemental response factors and the Compton Ka peak to normalize for matrix discrepancies. This simple approach to XRF analysis circumvents the need to acquire matrix-matched standardsfor either empirical coefficients orfundamen-tal parameter methods of calibration. Preliminary results show that response factor/Compton Ka peak normalization is a promising approach when screen­ing for these metals in soils, dust, paint chips and incinerated sludge. DATE DUE GAYLORD PRINTED IN U.S.A. For conversion of SI metric units to U.S./British customary units of measurement consult ASTM Standard E380-89a, Standard Practice for Use of the International System o f Units, published by the American Society for Testing and Materials, 1916 Race St., Philadelphia, Pa. 19103. ,¿3 sOo.W'^o iw Y