NCD986187094_20070201_Reasor Chemical Company_FRBCERCLA LTRA_Performance Standards Verification Plan Revision 1-OCR

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REASOR CHEMICAL SUPERFUND Sl1j
1
. , .
Castle Hayne, New Hanover County, North Caroli'na~
NCD986187094 _'}/
. '-1/ MAI"/ 1 9 ... 2 ' :-:---. J~-,.
PERFORMANCE STANDARDS VERIFICATION PLAN
REVISION I
February 2007
Prepared for:
United States Environmental Protection Agency
Region IV
61 Forsyth Avenue, SW
Atlanta, GA
Prepared by: ·
Apex Companies, LLC
811 Burke Street
Winston-Salem, North Carolina
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TABLE OF CONTENTS
1.0 INTRODUCTION ........................................................................................................................... I
1.1 Facility Location ........................................................................................................................... I
1.2 Historic Property Use and Ownership ...................................................................................... , .... I
1.3 General Site Layout ...................................................................................................................... I
1.4 Results of Investigations ............................................................... _. ............................................... 2
2.0 FIELD SAMPLING AND ANALYSIS PLAN ............................................................................. 3
2.1 Purpose .......................................................................................................................................... 3
2.2 Sampling Locations.................. . ................................................................ 3
2.3 Sampling Collection Procedurcs ................................................................................................... 3
2.4 Sample Iden ti lleation Procedures ..................... .. ....................... 4
2.5 Analytical Methods ........ 5
2.6 Sample Packaging and Shipping Procedures ...................... G
2.7 Field Sampling Equipment Decontamination Procedures............................... . ...................... 6
2.8 Sample/Field Activity Documentation Procedures.. .. ................ 6
2.9 Field Screening.......... .6
2.9.1 Organic Vapor Screening ............ 6
2.9.2 Tcmrcraturc. pH. and Conductivity Measurements... . .. 7
2.9.3 X-Ray fluorescence Screening ...... 7
3.0 QUALITY ASSURANCE/CONTROL PLAN ............................................................................. 8
3.1 Field Instrument Calibration and Preventive Maintenance ........................................................... 8
3.2 Quality Assurance/Quality Control Sample Collection ................................................................ 8
3.2.1 Equipment Blanks ................................................................................................................. 8
3.2.2 Trip Blanks ............................................................................................................................ 9
3.2.3 Field Blank Samples ............................................................................................................. 9
3.2.4 Duplicate Samples ............................................................................................................... I 0
3.2.5 Matrix Spike/Matrix Spike Duplicate Volume Requirements ............................................ 10
3.3 Organization of Field Sampling Team ........................................................................................ 10
3.4 Contract Laboratory Quality Assurance/Quality Control Procedures ......................................... I 0
FIGURES
FIGURE I
FIGURE 2
LIST OF TABLES
TABLE I
Location Map
Detailed Site Layout
Sample/Analytical Testing List
LIST OF ATTACHMENTS
APPENDIX A EPA Method 6200 XRF -Field Screening
APPENDIX B QA/QC Manual Analytical Services, Inc. (Electronic Submittal)
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Performance Standards Verification Plan -Revision I
Reasor Chemical Site Remediation -Castle 1/ayne, North Carolina
EPA ID Number NCD9860!87094
1.0 INTRODUCTION
February 2007
Section I
This Performance Standards Verification Plan (PSVP) presents the procedures and protocols required for
implementing the field sampling tasks associated with the remediation of the Reasor Chemical Supcrfund
Site (Site) in Castle Hayne, New Hanover County, North Carolina. Implementation of the PS_VP will
ensure that sufficient data, both qualitative and quantitative, will be available at the completion of the
remedial action to confinn the completion of the remedial action compared to data quality objectives
presented in the Record of Decision and any amendments. The specific tasks associated with sampling
locations, sampling depths, sampling methods and required analytical testing are included in the first
section ofthc PSVP under the heading of Field Sampling and Analysis Plan (FSAP). The analytical
protocols to be used for the analysis of samples collected under the field sampling tasks arc presented in
the Quality Assurance l)rojcct Plan (QAPP) which is included in the second section or this document.
This PSVP has been prepared in accordance with the United States Environmental Protection Agency
(EPA) issued Consen/ Decree (CD) and S1a1eme111 of Work for llemedial Aclio11 (SOW), both dated
October 2006.
I.I Facility Luc~1tion
The Site is located in Castle Hayne, New Hanover County, North Carolina at 5100 North College Road
just southeast of the junction of United States Highway 117 and North Carolina Route 132 within a 52.93
acre tract of vacant lru1d (Figure I). Access to the Site is via a dirt access road with a lockable gate.
1.2 Historic Property Use and Ownership
Prior to 1959, the property consisted of woodlands with a sniall creek through the property. Between
1959 until December I, 1971 the Site was operated and owned by Reasor Chemical Company and was
used for the processing of wood stumps for the recovery of pine products. These products included
turpentine, pine rosin, pine oil, camphor, pine tar and charcoal. The Site was then purchased by the
Martin Marietta Company (now Martin Marietta Materials). A fire and possible explosion occurred at the
Site on April 7, 1972 in which most of the Site buildings were damaged or destroyed. In 1986, the
property was sold to Hilda C. Dill and Jane C. Sullivan. Since 1972, the property has been vacant.
1.3 General Site Layout
Remnants of the former pine tree processing are evident at the Site. Certain buildings remain standing as
well as tank cradles and four surface impoundments (Ponds I through 4) which are believed to have been
part of the processing operation. There arc also areas where surface disposal of copper scrap occurred
(Copper Scrap Arca), a pipe shop where surface disposal of pipe materials occurred (Pipe Shop Arca),
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Perfor'!'ance Standards Verification Plan -Revision I February 2007
Reasor Chemical Site Remediation -Castle llayne, North Carolina
EPA ID Number NCD9860/87094 Section 1
and a swalc where drums containing unknown materials where stored and/or disposed (Drum Disposal
Arca). See Figure 2 for a detailed layout of the Site showing these areas. ·
1.4 Results of Investigations
Three government agencies, State of North Carolina Department of Environment and Natural Resources
(NCDENR), The Agency for Toxic Substances and Disease Registry (A TSDR) and EPA Region IV, have
performed/overseen investigations at the Site covering the environmental issues resulting from the former
operations.
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These investigations have included:
Preliminary Assessment Reconnaissance July 1991 (NCDENR);
Site Inspection November 1994 (NCDENR);
Remedial Investigation December 1999 (EPA):
Feasibility Study July 2002 (EPA);
Record of Decision September 2002 (EPA)
Data Evaluation Summa,y Rcpon July 2003 (EPA);
Design Criteria Report July 2003 (EPA):
Remedial Design January 2004 (F.PA);
Public Health Assessment February 2004 (A TSDR)
The Record of Decision and amendments to it which were made part of the Consent Decree (ROD)
formally presented the results of the investigations and established the following as the remedial actions
warranted at the Site:
• Ponds I through 4 -Removal, treatment and disposal of approximately 500,000
gallons of water;
• Ponds I through 4 -Removal and off-site disposal of approximately 1,250 cubic
yards of sediment; ,
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Scrap Copper Arca -Removal and off-site disposal of approximately 95 cubic yards
of soil;
Pipe Shop Arca -Removal and off-site disposal of approximately 30 cubic yards of
soil;
Drum Disposal Area -Removal and off-site disposal of drums and approximately
225 cubic yards of soil/residuals;
Placement of alkaline material onto the soils in the Drum Disposal Area;
Five-year duration annual sampling and analysis of existing groundwater monitoring
wells MW-7S and MW-7D for the presence of aluminum;
Closure of remaining existing wells on Site in accordance with State of North
Carolina regulations; and
Institutional Contro_ls/Land Use Restrictions
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Performance Standards Verification Plan -Revision J
ReaSor Cl,emica/ Site Remediation -Castle 1/ayne, North Carolina
EPA ID Number NCD9860187094
2.0 FIELD SAMPLING AND ANALYSIS PLAN
2.1 Purpose
February 2007
Section 2
Apex has prepared the following field sampling and analysis plan (FSAP) to document locations, and the
procedures for collection and analysis of various samples to be collected during the remediation of the
Site. The following sections provide details on our proposed sample locations, sample collection
procedures, sample identification procedures, analytical methods to be used for each sample, sample
shipping methods, field equipment decontamination procedures and the field documentation procedures.
Procedures for obtaining and recording various field data arc also included in this section.
2.2 Sampling Locations
Sampling locations arc sub-divided into two categories. The fir.st sampling group includes the locations
for samples needed for classification and profiling of removed materials and for permit compliance
purposes. The second group of sJmplc:,; involves the lol'.:nions needed to colllirm complctio1i of the
remediation to the requirernen.ts specified in the ROD. Confirmation samples will consist of composite
samples collected from individual I-foot square sampling locations for each area. The quantity of
composite samples per area and the respective analyses to be pcrfonncd are shown on Table I. The
loca.tions for confinnation sample collection are shown on Figure 2.
2.2.1 Soil Remediation Areas
The sampling plan calls for the collection of composite samples of the in-place residual soils after
excavation activities take place. For the Scrap Copper and Pipe Shop areas, one composite sample from
each area·is to be collected. For the Drum Disposal Area, three composite samples arc to be collected.
Specific target locations for the collection of each sample are shown on Figure 2.
2.2.2 Ponds
For each of the four ponds, the sampling plan calls for the collection of four composite samples of the
residual soils after removal of the pond water and sediment. For each pond, the location of the composite
samples will be the comer of the pond bottom adjacent to the sidewall/bottom junction.
2.3 Sampling Collection Procedures
Apex is proposing to use the sample collection procedures and equipment listed in the latest edition of the
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Perf(Jrmance Standards Verification Plan -Revision I February 2007
Reasor Chemical Site Remediation -Ca:ille Hayne, North Carolina
EPA ID Number NCD9860/87094 Section 2
EPA publication Environmen1al Investigations Standard Operating Procedures and Quality Assurance
Manual (EISOPQA M). Since the soil and sediment samples will be collected from surface or very
shallow(< 6-inch depth) locations, Apex is proposing to use trowels and field containers such as bowls
for sampling.· These items will either be single use disposables or manufactured from either Teflon or
stainless steel which allow for field decontamination between uses. Both classification/profiling samples
and confirmation samples will be collected and composited into field containers prior to placement into
laboratory-provided sample bottles/jars. Composite samples will be collected from I -foot square areas
where samples arc to be collected.· The following is the procedure to be used in collecting confirmation
samples in soils and sediments:
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Placement of I-foot square template at the sample location and marking comers with
temporary flagging (flagging will be used for surveying);
Removal of all soil/sediment within the marked area to a depth of 3-inchcs using a
disposable trowel or stainless steel spoon;
Placement of removed soil into stainless steel bowl;
Cicntlc mixing of collected sample and immediate placement of the sample into the
laboratory-provided containers; and
Ice the sample container after labeling and prepare fOr shipment.
Samph.· ldcni-ificalion Procedures
Each sample collected will be designated by an alphanumeric code that will identify the area of remedial
action, type of sampling location (profiling/confirmation), the specific location, the matrix sampled and a
specific sample designation (identifier). Site-specific procedures arc described below.
Sample identifications will contain a sequential code consisting of four segments. The first segment will
!dcntify the sample type. There arc three types of samples forecasted to be collected at the Site. Location
will identify the specific remedial action area being sampled. Matrix defines the matrix from which the
sample is collected. The specific sampling location will be identified using a two-digit number which
will change with each sample collected from the same area. The laboratory note identifies supplemental
samples, such as blanks and duplicates.
The following is a general guide for sample identification:
Sample Type
WP
SAMPLE TYPE
Location/Matrix
PISD
WP= Waste· Profiling
LB = Laboratory Blanks
Sample Location
01
Laboratory Note
FD
PC= Permit Compliance CF= Confirmation
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Performance Standards Verification Plan -Revision 1
Reasor Chemical Site Remediation -Castle HaylJe, North Carolina
EPA ID Number NCD9860187094
LOCATION
Pl= Pond I
= Pond 4
P2 = Pond 2
February 2007
Section 2
P3 = Pond 3 P4
DD = Drum Disposal Area CA = Copper Area
=MW7S
PP= Pipe Shop 7S
7D=MW7D
MATRIX TYPE:
MW= Monitoring Well
Water
GW = Ground Water
Water
SAMPLE LOCATION
Spcci fie location
LABORATORY NOTE
Fl3 = Field Blank
TB= Trip Blank
WW= Water Treatment
SD= Sediment Sample SW Surface
SO= Soil FW Field
EB= E4uipment Blank FD= Field Duplicate
A cumulative sampling master log will be maintained as the remedial action progresses. The sample
logbook will contain the sample number, sample date/time, sampling team, and chain of custody number.
2.5 Analytical Methods
Two different classifications of samples arc being collected and analyzed by laboratories during the Site
remediation. The first and most important group involves confirmation samples to provide proof of
remedial action meeting the requirements of the ROD. The second group of samples involves either
waste profiling for dispo_sal purposes or pcnnit compliance.
The confirmation samples will be analyzed for the specific Contaminants of Concern listed in the ROD
for each area. Sample analytical methods will follow the EPA Contract Laboratory Protocol.
The waste profiling/pennit compliance samples will be analyzed for the specific physical properties or.
chemicals in accordance with the latest revision of EPA publication SW-846 -Test Method, for·
Evaluating Solid Wastes. The quality control procedures listed in the ·publication will be used during
laboratory analysis of these samples.
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PerjiJrmance Standards Verification Plan -Revision I
Reasor Chemical Site Remediation -Castle Hayne, North Carolina
EPA ID Number NCD9860187094
2.6 Sample Packaging and Shipping Procedures
February 2007
Section 2
Samples will be packaged and shipped using chain-of-custody forms, sample labels, custody seals, and
other sample documents to be filled out as specified. Samples will be shipped within 24 hours of
collection by an overnight carrier.
2.7 Field Sampling Equipment Decontamination Procedures
As-presented below, all field sampling equipment will be decontaminated prior to sampling. Equipment
leaving the Site will also be decontaminated as called for in the Remedial Action Work Plan. All
decontamination activities will be completed at the dedicated decontamination area.
Unless otherwise specified, all non-dedicated sampling equipment utilized to obtain environmental
samples will be decontaminated between sampling points as follows per EISOPQAM:
2.8
I. \Vash with non-phosphate detergent;
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Tap water rinse;
De-ionized/distilled and organic free waler rinse;
Pcsticiclc-gruclc isopropanol rinse:
Double rinse with dt,::.ionized/distillcd organic-free water; and
Cover with plastic or wrap iii aluminum foil for overnight storage.
Sample/Field Activity Documentation Procedures
The sample team or individual performing a particular sampling act1v1ty is required to keep a field
notebook. The field notebook will be filled out at the location of sample collection immediately after
sampling. It will contain sample descriptions including: sample number, sample collection time, sample
location, sample description, sampling and sample preservation methods used, daily weather conditions,
field measurements, name of sampler, and other Site-specific observations. The field notebook will
contain any deviations from protocol, visitors' names, or community contacts made during samplin_g,
geologic and other Site-specific information that the Field Sample Team Leader warrants as noteworthy.
2.9 Field Screening
2.9.l Organic Vapor Screening
As part of the Health and Safety monitoring program, field screening for organic compounds will be
performed using a photo-ionization detector (PIO). Measurements will be taken in the breathing zone
during remediation activities and at the surface of each soil sample during collection.
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Performance Standards Verification Plan -Revision I
Reasm Chemical Site Remediation -Castle 1/ay11e, North Carolina
EPA ID Number NCD9860/87094
2.9.2 Temperature, pH, and Conductivity Measurements
February 2007
Section 2
Field measurements of conductivity, temperature, turbidity, and pH will be taken and recorded during the
sampling of the two groundwater monitoring wells. Since low-flow sampling technique will be used to
sample the two monitoring wells, the field measurements of these parameters will be the "trigger" as to
when the groundwater conditions in the well have reached equilibrium and sample collection can occur.
The complete pr°occdure for the low-flow sampling of the two groundwater monitoring wells is found the
Site's Operations and Maintenance Manual, prepared by Apex.
Each instrument will be checked and calibrated before sampling at each location and at the beginning and
end of each day, using standard solutions having known values. Field meters used during sampling (pH,
turbidity, and specific conductance meters) will be checked to ensure proper calibration and precision
response before initiation of the field program. A log that documents problems experienced with the
instrument, corrective measures taken, battery replacement dates, when used, and by whom, will be
maintained for each meter and thermometer. All equipment used during field sampling will be examined
to certify that it is in operating condition. This includes checking the manufacturer's operating manuals
:mcl the instructions with each instri1mcnt.
2.9.3 X-Rav Fluorescence Screcnino
For the remedial areas where metals are constituents of concern, Apex will use an X-Ray fluorescence
. monitor to provide "real-time" field measurements of the in-place metals concentrations as the removal
actions take ·place. The use of this evolving technology to provide this field screening is documented in
EPA Method 6200 as published in SW-846. (EPA Method 6200 is included with this plan in Appendix
A.) This process will be used only for screening purposes and will be supplemented by the confirmation.
samples described earlier.
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Performance Standards Verifil:atfon Plan-Revi!.;ion I
Reasor Chemical Site Remediation -Castle Hayne, North Carolina
EPA ID Number NCD9860/87094
3.0 QUALITY ASSURANCE/CONTROL PLAN
February 2007
Section 3
This section addresses the quality assurance and control procedures to be used during the remedial action
at the Site.
3.1 · Field Instrument Calibration and Preventive Maintenance
The Field Sampling Leader is responsible for assuring that a master instrument calibration/maintenance
log will be maintained for each measuring device. Each log will include at least the following
information, where applicable.
3.2
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name of device and/or instrnmcnt calibrated
device/instrument serial and/or I.D. number
• frequency or calibration
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date of calibration
results of calibration
name· of person performing the calibration
identification oi"thc calibration gas (OVA, PIO, CG!)
• buffer solutions (pH meter only)
Quality Assurance/Quality Control Sample Collection
Guidance on the collection of QA/QC samples is presented below.
3.2.1 Equipment Blanks
Equipment blanks will be taken to evaluate potential cross-contamination of samples due to the repeated
use of the same sampling equipment. Equipment blank samples will be performed on the following
sampling equipment; bowls, spoons, and pans used to collect and/or homogenize consecutive samples.
The frequency of equipment blanks taken is IO percent.
Equipment blanks will be obtained prior to the occurrence of any field sampling events being used for
confirmation of remedial action. The equipment blank will be obtained by pouring de-ionized water over
a particular piece of sampling equipment and into a sample container. For all sampling equipment, an
initial equipment blank, collected prior to use, will be collected and analyzed to ensure that s_ampling
equipment is clean prior to initiating sampling activities. Laboratory prepared and provided glass jars will
be used for organic blanks, and polyethylene jars will be used for metal blanks. When collecting
equipment blanks for volatile fractions, a separate aliquot of water must be used. The equipment blanks
as well as the trip blanks will accompany field personnel to the sampling location. The equipment blanks
will be analyzed in accordance with collected sample analytical and will be shipped with the samples
taken subsequently that day.·
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Performance Standards Verification Plan -Revision I February 2007
Reasor Chemical Site Remediation -Castle Hayne, North Carolina
EPA ID Number NCD9860187094
Equipment blanks will be taken in accordance with the procedure described below:
3.2.2
I. Decontaminate sampler using the procedures specified in this plan.
2. Pour distilled/de-ionized water over the sampling equipment and collect the
rinseate water in the appropriate sample bottles.
3.
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Immediately place in a sample cooler and maintain at a temperature of 4 degrees
e until receipt by the laboratory.
Fill out sample log. labels and chain-of-custody fom1s, and record in field
notebook.
Trip Blanks
Section 3
A trip blank is an aliquot of de-ionized writer that is scaled in a sample bottle prior to initiation of each
day of fieldwork. The trip blank is used to determine if any cross-contamination occurs between aqueous
samples during shirmcnt. Trip blanks arc analyzed for aqueous volatile organic compounds (VOC) only.
Glass vials (40ml) with Teflon lids will be used for voe blanks. A trip blank will be prepared prior to
each day of field sampling for aqueous volatiles. If multiple coolers arc required to store and transport
aqueous VOC samples, each cooler must contain an individual trip blank. Trip blanks will accompany
only aqueous samples.
Trip blanks will be taken in accordance with the procedure described below:
3.2.3
I. Pour distilled/de-ionized water into two (2) laboratory provided and preserved
40-ml glass voe vials just to overflowing so that no air bubbles remain. Seal
the sample bottle so that no air bubbles are entrapped inside immediately place in
2.
sample cooler and maintain at 4'e until receipt by the laboratory.
Fill out sample log, labels and chain-of-custody fonns, and record in field
notebook. Place vials in cooler(s) to be stored and shipped with samples
collected that day.
Field Blank Samples
A field blank sample is obtained by filling laboratory prepared sample containers with distilled/de-ionized
water while conducting Site activities. Field Blank samples arc collected to ensure that ambient Site
conditions (emissions, dust, etc.) do not contribute to anomalous sample analytical results. One field
blank sample will be collected per day of sampling. Glass jars will be used for organic blanks, and
polyethylene jars will be used for metal blanks. Field blanks will be analyzed in accordance with Table I
and will be shipped with the samples taken subsequently that day.
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Performance Standards Verification Plan -Revision I
Reasor Chemical Site Remediation -Castle Hayne, North Carolina
EPA ID Number NCD9860/87094
3.2.4 Duplicate Samples
February 2007
Section 3
Duplicate samples will be analyzed to check laboratory reproducibility. of analytical data. At least ten
percent (one out of every IO field samples) of the total number of collected samples or one per analytical
batch, whichever is greater will be duplicated to evaluate the precision of the methods used. Duplicate
samples must be taken from each of the environmental matrices sampled. · Clarifying, one duplicate
sample shall be collected from the in-place soils in the four ponds; one duplicate sample shall be collected
from either of the soils underlying the Copper Scrap Arca or Pipe Shop Arca; and one duplicate sample
collected from the Dru1i1 Disposal Arca.
3.2.5 Matrix Spike/Matrix Spike Duplicate Volume Requirements
Matrix spike/matrix spike duplicates (MS/MSD) for organic and inorganic analyses arc to he performed at
frequency of IO percent. To ensure the laboratory has sufficient volume for MS/MSD analysis, triple
sample volume must be submitted for aqueous organic extractable and volatile samples once per every ten
samples in a sample delivery group, per matrix. Clarifying, one MS/MSD sample shall be collected from
the in-place soils in the four ponds; one duplicate sample shall be collected from either of the soils
underlying the Copper Scrap i\rca or Pipe Shop Arca; and one duplicate sample collected from the Drum
Disposal Arca.
3.3 Organization of Field Sampling Team
San1pling activities at the Site, including the sample equipment decontamination, shall be performed by
the Field Sample Team Leader. This Apex employee shall have a minimum of three years of field
experience and have direct experience in collecting samples, preparing Chain-of-Custodies, and
completing field activity documentation reports. The Field Sample Team Leader will report directly to
the Apex Project Coordinator/Project Manager.
3.4 Contract Laboratory Quality Assurance/Quality Control Procedures
Apex will be using Analytical Services, Incorporated to provide laboratory analysis of confirmation
samples collected at the Site. The laboratory's Quality Assurance/Quality Control Manual is provided
with this PSVP in electronic form (with EPA concurrence) in Appendix B.
To provide an independent Quality Assurance review, the Field Sampling Leader shall report to the
Project Coordinator. This team member will not only perform the sampling activities specified, but in
conjunction with the s_elcctcd laboratories quality control officers will also serve as the reviewer of field
remediation activities and laboratory data to assure that the remediation is proceeding in accordance with
RAP and the ROD and amendments. This team member will have complete authority to accept or reject
laboratory data that docs not meet the quality control requirement for the project.
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Performance Standards Verification Plan -Revfaion I
Reasor Chemical Site Remediation -Castle Hayne, North Carolina
£/'A ff) Number NCD9860187094
February 2007
Section 3
Analytical services for waste profiling/permit compliance services will be provided by a laboratory
certified by the State of North Carolina. Apex is currently considering the use of either Prism
Laboratories or Pace Analytical Services, both of which arc located in metropolitan Charlotte, North
Carolina.
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13 I
- - - --
WP
WP
WP
CF
CF
CF
CF
CF
CF
LB
CF
CF
CF
LB
CF
CF
CF
CF
LB
LB
PC
CF
CF
LB
CF
-l!!!!!!!!!I l!!!!!I !!!!I == liiiiiii liiiiil liii!i!i!I -
Table 1 -Sample/Analytical Testing List
Reasor Chemical Site
P1 SD 01
P2 SD 01
P3 SD 01
P4
DD
CNPP
P1
P2
P3
P4
· Pi
Pi
Pi
DD
DD
DD
DD
CA
pp
CA or PP
CA or PP
CA or PP
All
WW
7S
7D
7S/7D
7i
SD
so so so so so so so so so so so so
so so so so so
FW
FW
SW
GW
GW
FW
GW
01
01
01
01
01
01
01
01
01
01
01
01
01
01
01
01
01
01
01
xx
xx
01
01
01
01
BAP,BF,DBA,SB,CU,PB
BAP,BF,DBA,SB,CU,PB
BAP,BF,DBA,SB,CU,PB
BAP,BF,DBA,SB,CU,PB
BAP,BF,DBA,SB,CU,PB
BAP,BF,DBA,SB,CU,PB
SVOC,TAL
BAP,BF,DBA
BAP,BF,DBA
BAP,BF,DBA
SVOC
BAP,BF,SB,CU,PB
SB.CU.PB
Match location
Match locntion
SVOC,TAL
SVOC,TAL
SVOC,TAL
AL
AL
AL
AL
Landfill Profiling
Landfil! Profiling
Landfill Profiling
Landfill Profiling
Landfill Profiling
Landfill Profilin . Com osite of both areas
Composite of 4 locations
Composite of 4 locations
Composite of 4·!ocations
Composite of 4 locations
Field duplicate from one pond
Matrix spike & duplicate from one pond
Field blank
Composite of 3 locations
Field duplicate
Matrix spike & duplicate
Field blank
Composite of 2 locations
Composite of 2 locations
Field duplicate
Matrix spike & duplicate
Field blank
Equipment blanks -as needed
One per 50k aliens
1st round groundwater sampling
1st round groundwater sampling
Field blank groundwater sampling
Field duplicate groundwater sampling
Notes: BAP = Benzo(a)pyrene AL= Aluminum
BF= Benzo (b or k) fluoranthene
DBA = Dlbenzo (a,h) anthracene
SB = Antimony
CU= Copper
PB"' Lead
SVOC = Semivolatilo organics
TAL = Target analyte list
WP= Waste Profiling
PC= Permit compliance
P1, P2, PJ, P4 = Process ponds 1 through 4
CA= Copper Scrap Area
PP = Pipe Shop Area
DD= Drum Disposal Area
'WW= Treated surface water
71 = MW.7S or MW•7D groundwater
CF= Confirmation sc1mple
LB= Laboratory sample {blank)
Groundwater sampling Includes field measuring of temperature, conductivity, pH. turbidity
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Al'l'Ei\'DIX A
EPA METHOD 6200 -XRF FIELD SCREENING
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METHOD 6200
FIELD PORTABLE X-RAY FLUORESCENCE SPECTROMETRY FOR THE
DETERMINATION OF ELEMENTAL CONCENTRATIONS IN SOIL AND SEDIMENT
1.0 SCOPE AND APPLICATION
1.1 This method is applicable to the in situ and intrusive analysis of the 26 analytes listed
in Table 1 for soil and sediment samples. Some common elements are not listed in Table 1
because they are considered "light" elements that cannot be detected by field portable x-ray
fluorescence (FPXRF). They are: lithium, beryllium, sodium, magnesium, aluminum, silicon, and
phosphorus. Most of the analytes listed in Table 1 are of environmental concern, while a few others
have interference effects or change the elemental composition of the matrix, affecting quantitation
of the analytes of interest. Generally elements of atomic number 16 or greater can be detected and
quantitated by FPXRF.
1.2 Detection limits depend on several factors, the analyte of interest, the type of detector
used, the type of excitation source, the strength of the excitation source, count times used to
irradiate the sample, physical matrix effects, chemical matrix effects, and interelement spectral
interferences. General instrument detection limits for analytes of interest in environmental
applications are shown in Table 1. These detection limits apply to a clean matrix of quartz sand
(silicon dioxide) free of interelement spectral interferences using long (600-second) count times.
These detection limits are given for guidance only and will vary depending on the sample matrix,
which instrument is used, and operating conditions. A discussion of field performance-based
detection limits is presented in Section 13.4 of this method. The clean matrix and field
performance-based detection limits should be used for general planning purposes, and a third
detection limit discussed, based on the standard deviation around single measurements, should
be used in assessing data quality. This detection limit is discussed in Sections 9.7 and 11.3.
1.3 Use of this method is restricted to personnel either trained and knowledgeable in the
operation of an XRF instrument or under the supervision of a trained and knowledgeable individual.
This method is a screening method to be used with confirmatory analysis using EPA-approved
methods. This method's main strength is as a rapid field screening procedure. The method
detection limits (MDL) of FPXRF are above the toxicity characteristic regulatory level for most
RCRA analytes. If the precision, accuracy, and detection limits of FPXRF meet the data quality
objectives (DQOs) of your project, then XRF is a fast, powerful, cost effective technology for site
characterization.
2.0 SUMMARY OF METHOD
2.1 The FPXRF technologies described in this method use sealed radioisotope sources
to irradiate samples with x-rays. X-ray tubes are used to irradiate samples in the laboratory and
are beginning to be incorporated into field portable instruments. When a sample is irradiated with
x-rays, the source x-rays may undergo either scattering or absorption by sample atoms. This later
process is known as the photoelectric effect. When an atom absorbs the source x-rays, the incident·
radiation dislodges electrons from the innermost shells of the atom, creating vacancies. The
electron vacancies are filled by electrons cascading in from outer electron shells. Electrons in outer
shells have higher energy states than inner shell electrons, and the outer shell electrons give off
energy as they cascade down into the inner shell vacancies. This rearrangement of electrons
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results in emission of x-rays characteristic of the given atom. The emission of x-rays, in this
manner, is termed x-ray fluorescence.
Three electron shells are generally involved in emission of x-rays during FPXRF analysis of
environmental samples: the K, L, and M shells. A typical emission pattern, also called an emission
spectrum, for a given metal has multiple intensity peaks generated from the emission of K, L, or M
shell electrons: The most commonly measured x-ray emissions are from the K and L shells; only
metals with an atomic number greater than 57 have measurable M shell emissions.
Each characteristic x-ray line is defined with the letter K, L, or M, which signifies which shell
had the original vacancy and by a subscript alpha (a) or beta (13), which indicates the higher shell
from ·which electrons fell to fill the vacancy and produce the x-ray. For example, a K0 line is
produced by a vacancy in the K shell filled by an L shell electron, whereas a Kp line is produced by
a vacancy in the K shell filled by an M shell electron. The K0 transition is on average 6 to 7 times
more probable than the Kp transition; therefore, the K0 line is approximately 7 times more intense
than the Kp line for a given element, making the K0 line the choice_ for quantitation purposes.
The K lines for a given element are the most energetic lines and are the preferred lines for
analysis. For a given atom, the x-rays emitted from L transitions are always less energetic than
those emitted from K transitions. Unlike the K lines, the main L emission lines (L0 and Lp) for an
element are of nearly equal intensity. The choice of one or the other depends on what interfering
element lines might be present. The L emission lines are useful for analyses involving elements
of atomic number (Z) 58 (cerium) through 92 (uranium).
An x-ray source can excite characteristic x-rays from an element only if the source energy is
greater than the absorption edge energy for the particular line group of the element, that is, the K
absorption edge, L absorption edge, or M absorption edge energy. The absorption edge energy
is somewhat greater than the corresponding line energy. Actually, the K absorption edge energy
is approximately the sum of the K, L, and M line energies of the particular element, and the L
absorption edge energy is approximately the sum of the L and M line energies. FPXRF is more
sensitive to an element with an absorption edge energy close to but less than the excitation energy
of the source. For example, when using a cadmium-109 source, which has an excitation energy
of 22.1 kiloelectron volts (keV), f=PXRF would exhibit better sensitivity for zirconium which has a
Kline energy of 15.7 keV than tci chromium, which has a Kline energy of 5.41 keV.
2.2 Under this method, inorganic analytes of interest are identified and quantitated using
a field portable energy-dispersive x-ray fluorescence spectrometer. Radiation from one or more
radioisotope sources or an electrically excited x-ray tube is used to generate cha"racteristic x-ray
emissions from elements in a sample. Up to three sources may be used to irradiate a sample.
Each source emits a· specific set of primary x-rays that excite a corresponding range of elements
in a sample. When more than one source can excite the element of interest, the source is selected
_ according to its excitation efficiency for the element of interest.
For measurement, the sample is positioned in front of the probe window. This can be done
in two manners using FPXRF instruments: in situ or intrusive. If operated in the in situ mode, the
probe window is placed in direct contact with the soil surface to be analyzed. When an FPXRF
instrument is operated in the intrusive mode, a soil or sediment sample must be collected,
prepared, and placed in a sample cup. The sample cup is then placed on top of the window inside
a protective cover for analysis.
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Sample analysis is then initiated by exposing the sample to primary radiation from the source.
Fluorescent and backscattered x-rays from the sample enter through the detector window and are
converted into electric pulses in the detector. The detector in FPXRF instruments is usually either
a solid-state detector or a gas-filled proportional counter. Within the detector, energies of the
characteristic x-rays are converted into a train of electric pulses, the amplitudes of which are linearly
proportional to the energy of the x-rays. An electronic multichannel analyzer (MCA) measures the
pulse amplitudes, which is the basis of qualitative x-ray analysis. The number of counts at a given
energy per unit of time is representative of the element concentration in a sample and is the basis
for quantitative analysis. Most FPXRF instruments are menu-driven from software built into the
units or from personal computers (PC).
The measurement time of each source is user-selectable. Shorter source measurement times
(30 seconds) are generally used for initial screening and hot spot delineation, and longer
measurement times (up to 300 seconds) are typically used to meet higher precision and accuracy
requirements.
FPXRF instruments can be calibrated using the following methods: internally using
fundamental parameters determined by the manufacturer, empirically based on site-specific
calibration_ standards (SSCS), or based on Compton peak ratios. The Compton peak is produced
by backscattering of the source radiation. Some FPXRF instruments can be calibrated using
multiple methods.
3.0 DEFINITIONS
3.1 FPXRF: Field portable x-ray fiuorescence.
3.2 MCA: Multichannel analyzer for measuring pulse amplitude,_
3.3 SSCS: Site specific calibration standard.
3.4 FP: Fundamental parameter.
3.5 ROI: Region of interest.
3.6 SRM: Standard reference material. A standard containing certified amounts of metals
in soil or sediment.
3. 7 eV: Electron Volt. A unit of energy equivalent to the amount of energy gained by an
electron passing through a potential difference of one volt.
3.8 Refer to Chapter One and Chapter Three for additional definitions.
4.0 INTERFERENCES
4.1 The total method error for FPXRF analysis is defined as the square root of the sum ·
of squares of both instrument precision and user-or application-related error. Generally, instrument
precision is the least significant source of error in FPXRF analysis. User-or application-related
error is generally more significant and varies with each site and method used. Some sources of
interference can be minimized or controlled by the instrument operator, but others cannot.
Common sources of user-or application-related error are discussed below.
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4.2 Physical matrix effects result from variations in the physical character of the sample.
These variations may include such parameters as particle size, uniformity, homogeneity, and
surface condition. For example, if any analyte exists in the form of very fine particles in a coarser-
grained matrix, the analyte's concentration measured by the FPXRF will vary depending on how
fine particles are distributed within the coarser-grained matrix. If the fine particles "settle" to the
bottom .of the sample cup, the analyte concentration measurement will be higher than if the fine
particles are not mixed in well and stay on top of the coarser-grained particles in the sample cup.
One way to reduce such error is to grind and sieve all soil samples to a uniform particle size thus
reducing sample-to-sample particle size variability. Homogeneity is always a concern when dealing
with soil samples. Every effort should be made to thoroughly mix and homogenize soil samples
before analysis. Field studies have shown heterogeneity of the sample generally has the largest
impact on comparability with confirmatory samples.
4.3 Moisture content may affect the accuracy of analysis of soil and sediment sample
analyses. When the moisture content is between 5 and 20 percent, the overall error from moisture
may be minimal. However, moisture content may be a major source of error when analyzing
samples of surface soil or sediment that are saturated with water. This error can be minimized by
drying the samples in a convection or toaster oven. Microwave drying is not recommended
because field studies have shown that microwave drying can increase variability between FPXRF
data and confirmatory analysis and because metal fragments in the sample can cause arcing to
occur in a microwave.
4.4 Inconsistent positioning of samples in front of the probe window is a potential source
of error because the x-ray signal decreases as the distance from the radioactive source increases.
This error is minimized by maintaining the same distance between the window an_d each sample.
For the best results, the window of the probe should be in direct contact with the sample, which
means that the sample should be flat and smooth to provide a good contact surface.
4.5 Chemical matrix effects result from differences in the concentrations of interfering
elements. These effects occur as either spectral interferences (peak overlaps) or as x-ray
absorption and enhancement phenomena. Both effects are common in soils contaminated with
heavy metals. As examples of absorption and enhancement effects; iron (Fe) tends to absorb
copper (Cu) x-rays, reducing the intensity of the Cu measured by the detector, while chromium (Cr)
will be enhanced at the expense of Fe because the absorption edge of Cr is slightly lower in energy
than the fluorescent peak of iron. The effects can be corrected mathematically through the use of
fundamental parameter (FP) coefficients. The effects also can be compensated for using SSCS,
which contain all the elements present on site that can interfere with one another.
4.6 When present in a sample, certain x-ray lines from different elements can be very
close in energy and, therefore, can cause interference by producing a severely overlapped
spectrum. The degree to which a detector can resolve the two different peaks depends on the
energy resolution of the detector. If the energy difference between the two peaks in electron volts
is less than the resolution of the detector in electron volts, then the detector will not be able to fully
resolve the peaks.
The most common spectrum overlaps involve the Kp line of element Z-1 with the K0 line of
element Z. This is called the K0/Kp interference. Because the K0:~ intensity ratio for a given
element usually is about 7:1, the interfering element, Z-1, must be present at large concentrations
to cause a problem. Two examples of this type of spectral interference involve the presence of
large concentrations of vanadium (V) when attempting to measure Cr or the presence of large
concentrations of Fe when attempting to measure cobalt (Co). The V Ka and Kp energies are 4.95
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and 5.43 keV, respectively, and the Cr K,, energy is 5.41 keV. The Fe Ka and Kp energies are 6.40
and 7.06 keV, respectively, and the Co K,, energy is 6.92 keV. The difference between the V K1 and
Cr Ka energies is 20 eV, and the difference between the Fe K1 and the Co Ka energies is 140 eV.
The resolution of the highest-resolution detectors in FPXRF instruments is 170 eV. Therefore, large
amounts of V and Fe will interfere with quantitation of Cr or Co, respectively. The presence of Fe
is a frequent problem because it is often found in soils at tens of thousands of parts per million
(ppm).
4.7 Other interferences can arise from KIL, K/M, and L/M line overlaps, although these
overlaps are less common. Examples of such overlap involve arsenic (As) Ka/lead (Pb) La and
sulfur (S) Ka/Pb Ma. In the As/Pb case, Pb can be measured from the. Pb L1 line, and As can be
measured from either the As Ka or the As K0 line; in this way the interference can be corrected. If
the As K1 line is used, sensitivity will be decreased by a factor of two to five times because it is a
less intense line than the As Ka line. If the As Ka line is used in the presence of Pb, mathematical
corrections within the instrument software can be used to subtract out the Pb interference.
However, because of the limits of mathematical corrections, As concentrations cannot be efficiently
calculated for samples with Pb:As ratios of 10: 1 or more. This high ratio of Pb to As may result in
no As being reported regardless of the actual concentration present.
No instrument can fully compensate for this interference. It is important for an operator to
understand this limitation of FPXRF instruments and consult with the manufacturer of the FPXRF
instrument to evaluate options to minimize this limitation. The operator's decision will be based
on action levels for metals in soil established for the site, matrix effects, capabilities of the
instrument, data quality objectives, and the ratio of lead to arsenic known to be present at the site.
If a site is encountered that contains lead at concentrations greater than ten times the concentration
of arsenic it is advisable that all critical soil samples be sent off site for confirmatory analysis by an
EPA-approved method.
4.8 If SSCS are used to calibrate an FPXRF instrument, the samples collected must be
representative of the site under investigation. Representative soil sampling ensures that a sample
or group of samples accurately reflects the concentrations of the contaminants of concern at a
given time and location. Analytical results for representative samples reflect variations in the
presence and concentration ranges of contaminants throughout a site. Variables affecting sample
representativeness include differences in soil type, contaminant concentration variability, sample
collection and preparation variability, and analytical variability, all of which should be minimized as
much as possible.
4.9 Soil physical and chemical effects may be corrected using SSCS that have been
analyzed by inductively coupled plasma (ICP) or atomic absorption (AA) methods. However, a
major source of error can be introduced if these samples are not representative of the site or if the
analy1ical error is large. Another concern is the type of digestion procedure used to prepare the soil
samples for the reference analysis. Analy1ical results for the confirmatory method will vary
depending on whether a partial digestion procedure, such as SW-846 Method 3050, or a total
digestion procedure, such as Method 3052 is used. It is known that depending on the nature of the
soil or sediment, Method 3050 will achieve differing extraction efficiencies for different analy1es of
interest. The confirmatory method should meet the project data quality objectives.
XRF measures the total concentration of an element; therefore, to achieve the greatest
comparability of this method with thereference method (reduced bias), a total digestion procedure
should be used for sample preparation. However, in the study used to generate the performance
data for this method, the confirmatory method used was Method 3050, and the FPXRF data
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compared very well with regression correlation coefficients (r often exceeding 0.95, except for
barium and chromium. See Table 9 in Section 17.0). The critical factor is that the digestion
procedure and analytical reference method used should meet the data quality objectives (DQOs)
of the project and match the method used for confirmation analysis.
4.10 Ambient temperature changes can affect the gain of the amplifiers producing
instrument drift. Gain or drift is primarily a function of the electronics (amplifier or preamplifier) and
not the detector as most instrument detectors are cooled to a constant temperature. Most FPXRF
instruments have a built-in automatic gain control. If the automatic gain control is allowed to make
periodic adjustments, the instrument will compensate for the influence of temperature changes on
its energy scale. If the FPXRF instrument has an automatic gain control function, the operator will
not have to adjust the instrument's gain unless an error message appears. If an error message
appears, the operator should follow the manufacturer's procedures for troubleshooting the problem.
Often, this involves performing a new energy calibration. The performance of an energy calibration
check to assess drift is a quality control measure discussed in Section 9.2.
If the operator is instructed by the manufacturer to manually conduct a gain check because
of increasing or decreasing ambient temperature, it is standard to perform a gain check after every
10 to 20 sample measurements or once an hour whichever is more frequent. It is also suggested
that a gain check be performed if the temperature fluctuates more than 10 to 20°F. The operator
should follow the manufacturer's recommendations for gain check frequency.
5.0 SAFETY
5. 1 Proper training for the safe operation of the instrument and radiation training should
be completed by the analyst prior to analysis. Radiation safety for each specific instrument can be
found in the operators manual. Protective shielding should never be removed by the analyst or any
personnel other than the manufacturer. The analyst should be aware of the local state and national
regulations that pertain to the use of radiation-producing equipment and radioactive materials with
which compliance is required. Licenses for radioactive materials are of two types; ( 1) general
license which is usually provided by the manufacturer for receiving, acquiring, owning, possessing,
using, and transferring radioactive material incorporated in a device or equipment, and (2) specific
license which is issued to named persons for the operation of radioactive instruments as required
by local state agencies. There should be a person appointed within the organization that is solely
responsible for properly instructing all personnel, maintaining inspection records, and monitoring
x-ray equipment at regular intervals. A copy of the radioactive material licenses and leak tests
should be present with the instrument at all times and available to local and ·national authorities
upon request. X-ray tubes do not require radioactive.material licenses or leak tests, but do require
approvals and licenses which vary from state to state. In addition, fail-safe x-ray warning lights
should be illuminated whenever an x-ray tube is energized. Provisions listed above concerning
radiation safety regulations, shielding, training, and responsible personnel apply to x-ray tubes just
as to radioactive sources. In addition, a log of the times and operating conditions should be kept
whenever an x-ray tube is energized. Finally, an additional hazard present with x-ray tubes is the
danger of electric shock from the high voltage supply. The danger of electric shock is as substantial
as the danger from radiation but is often overlooked because of its familiarity.
5.2 Radiation monitoring equipment should be used with the handling of the instrument.
The operator and the surrounding environment should be monitored continually for analyst
exposure to radiation. Thermal luminescent detectors (TLD) in the form of badges and rings are
used to monitor operator radiation exposure. The TLDs should be worn in the area of most
frequent exposure. The maximum permissible whole-body dose from occupational exposure is 5
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Roentgen Equivalent Man (REM) per year. Possible exposure pathways for radiation to enter the
body are ingestion, inhaling, and absorption. The best precaution to prevent radiation exposure
is distance and shielding.
5.3 Refer to Chapter Three for guidance on some proper safety protocols.
6.0 EQUIPMENT AND SUPPLIES
6.1 FPXRF Spectrometer: An FPXRF spectrometer consists of four major components:
(1) a source that provides x-rays; (2) a sample presentation device; (3) a detector that converts x-
ray-generated photons emitted from the sample into measurable electronic signals; and (4) a data
processing unit that contains an emission or fluorescence energy analyzer, such as an MCA, that
processes the signals into an x-ray energy spectrum from which elemental concentrations in the
sample may be calculated, and a data display and storage system. These components and
additional, optional items, are discussed below.
6.1.1 Excitation Sources: Most FPXRF instruments use sealed radioisotope
sources to produce x-rays in order to irradiate· samples. The FPXRF instrument may contain
between one and three radioisotope sources. Common radioisotope sources used for
analysis for metals in soils are iron (Fe)-55, cadmium (Cd)-109, americium (Am)-241, and
curium (Cm)-244. These sources may be contained in a probe along with a window and the
detector; the probe is connected to a data reduction and handling system by means of a
flexible cable. Alternatively, the sources, window, and detector may be included in the same
unit as the data reduction and handling system.
The relative strength of the radioisotope sources is measured in units of millicuries
(mCi). All other components of the FPXRF system being equal, the stronger the source, the
greater the sensitivity and precision of a given instrument. Radioisotope sources undergo
constant decay. In fact, it is this decay process that emits the primary x-rays used to excite
samples for FPXRF analysis. The decay of radioisotopes is measured in "half-lives." The
half-life of a radioisotope is defined as the length of time required to reduce the radioisotopes
strength or activity by half. Developers of FPXRF technologies recommend source
replacement at regular intervals based on the source's half-life. The characteristic x-rays
emitted from each of the different sources have energies capable of exciting a certain range
of analytes in a sample. Table 2 summarizes the characteristics of four common radioisotope
sources.
X-ray tubes have higher radiation output, no intrinsic lifetime limit, produce constant
output over their lifetime, and do not have the disposal problems of radioactive sources but
are just now appearing in FPXRF instruments An electrically-excited x-ray tube operates by
bombarding an anode with electrons accelerated by a high voltage. The electrons gain an
energy in electron volts equal to the accelerating voltage and can excite atomic transitions in
the anode, which then produces characteristic x-rays. These characteristic x-rays are emitted
through a window which contains the vacuum required for the electron acceleration. An
important difference between x-ray tubes and radioactive sources is that the electrons which
bombard the anode also produce a continuum of x-rays across a broad range of energies in
addition to the characteristic x-rays. This continuum is weak compared to the characteristic
x-rays but can provide substantial excitation since it covers a broad energy range. It has the
undesired property of producing background in the spectrum near the analyte x-ray lines
when it is scattered by the sample. For this reason a filter is often used between the x-ray
tube and the sample to suppress the continuum radiation while passing the characteristic
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x-rays from the anode. This filter is sometimes incorporated into the window of the x-ray tube.
The choice of accelerating voltage is governed by the anode material, since the electrons
must have sufficient energy to excite the anode, which requires a voltage greater than the
absorption edge of the anode material. The anode is most efficiently excited by voltages 2
to 2.5 times the edge energy (most x-rays per unit power to the tube), although voltages as
low as 1.5 times the absorption edge energy will work. The characteristic x-rays emitted by
the anode are capable of exciting a range of elements in the sample just as with a radioactive
source. Table 3 gives the recommended operating voltages and the sample elements excited
for some common anodes.
6.1.2 Sample Presentation Device: FPXRF instruments can be operated in two
modes: in situ and intrusive. If operated in the in situ mode, the probe window is placed in
direct contact with the soil surface to be analyzed. When an FPXRF instrument is operated
in the intrusive mode, a soil or sediment sample must be collected, prepared, and placed in
a sample cup. For most FPXRF instruments operated in the intrusive mode, the probe is
rotated so that the window faces upward. A protective sample cover is placed over the
window, and the sample cup is placed on top of the window inside the protective sample
cover for analysis.
6.1.3 Detectors: The detectors in the FPXRF instruments can be either solid-state
detectors or gas-filled, proportional counter detectors. Common solid-state detectors include
mercuric iodide (Hgl2), silicon pin diode and lithium-drifted silicon Si(Li). The Hgl2 detector
is operated at a moderately subambient temperature controlled by a low power thermoelectric
cooler. The silicon pin diode detector also is cooled via the thermoelectric Peltier effect. The
Si(Li) detector must be cooled to at least -90 °C either with liquid nitrogen or by thermoelectric
cooling via the Peltier effect. Instruments with a Si(Li) detector have an internal liquid nitrogen
dewar with a capacity of 0.5 to 1.0 liter. Proportional counter detectors are rugged and
lightweight, which are important features of a field portable detector. However, the resolution
of a proportional counter detector is not as good as that of a solid-state detector. The energy
resolution of a detector for characteristic x-rays is usually expressed in terms of full width at
half-maximum (FWHM) height of the manganese K, peak at 5.89 keV. The typical resolutions
of the above mentioned detectors are as follows: Hgl2-270 eV; silicon pin diode-250 eV;
Si(Li)-170 eV; and gas-filled, proportional counter-750 eV.
During operation of a solid-state detector, an x-ray photon strikes a biased, solid-state
crystal and loses energy in the crystal by producing electron-hole pairs. The electric charge
produced is collected and provides a current pulse that is directly proportional to the energy
of the x-ray photon absorbed by the crystal of the detector. A gas-filled, proportional counter
detector is an ionization chamber filled with a mixture of noble and other gases. An x-ray
photon entering the chamber ionizes the gas atoms. The electric charge produced is
collected and provides an electric signal that is directly proportional to the energy of the x-ray
photon absorbed by the gas in the detector.
6.1.4 Data Processing Units: The key component in the data processing unit of an
FPXRF instrument is the MCA. The MCA receives pulses from the detector and sorts them
by their amplitudes (energy level). The MCA counts pulses per second to determine the
height of the peak in a spectrum, which is indicative of the target analy1e's concentration. The
spectrum of element peaks are built on the MCA. The MCAs in FPXRF instruments have
from 256 to 2,048 channels. The concentrations of target analy1es are usually shown in parts
per million on a liquid crystal display (LCD) in the instrument. FPXRF instruments can store
both spectra and from 100 to 500 sets of numerical analy1ical results. Most FPXRF
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instruments are menu-driven from software built into the units or from PCs. Once the
data-storage memory of an FPXRF unit is full, data can be downloaded by means of an RS-
232 port and cable to a PC.
6.2 Spare battery chargers.
6.3 Polyethylene sample cups: 31 millimeters (mm) to 40 mm in diameter with collar, or
equivalent (appropriate for FPXRF instrument).
6.4 X-ray window film: Mylar™, Kaplan™, Spectrolene™, polypropylene, or equivalent; 2.5
to 6.0 micrometers (µm) thick.
6.5 Mortar and pestle: glass, agate, or aluminum oxide; for grinding soil and sediment
samples.
6.6 Containers: glass or plastic to store samples.
6.7 Sieves: 60-mesh (0.25 mm), stainless-steel, Nylon, or equivalent for preparing soil and
sediment samples.
6.8 Trowels: for smoothing soil surfaces and collecting soil samples.
6.9 Plastic bags: used for collection ·and homogenization of soil samples.
6.10 Drying oven: standard convection or toaster oven, for soil and sediment samples that
require drying.
7.0 REAGENTS AND STANDARDS
7 .1 Pure Element Standards: Each pure, single-element standard is intended to produce
strong characteristic x-ray peaks of the elemenfof interest only. Other elements present must not
contribute to the fluorescence spectrum. A set of pure element standards for commonly sought
analytes is supplied by the instrument manufacturer, if required for the instrument; not all
instruments require the pure element standards. The standards are used to set the region of
interest (ROI) for each element. They also can be used as energy calibration and resolution check
samples.
7.2 Site-specific Calibration Standards: Instruments that employ fundamental parameters
(FP) or similar mathematical models in minimizing matrix effects may not require SSCS. If the FP
calibration model is to be optimized or if empirical calibration is necessary, then SSCSs must be
collected, prepared, and analyzed.
7.2.1 The SSCS must be representative of the matrix to be analyzed by FPXRF.
These samples must be well homogenized. A minimum of ten samples spanning the
concentration ranges of the analytes of interest and of the interfering elements must be
obtained from the site. A sample size of 4 to 8 ounces is recommended, and standard glass
sampling jars should be used.
7.2.2 Each sample should be oven-dried for 2 to 4 hours at a temperature of less
than 150°C. If mercury is to be analyzed, a separate sample portion must remain undried,
as heating may volatilize the mercury. When the sample is dry, all large, organic debris and
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non representative material, such as twigs, leaves, roots, insects, asphalt, and rock should be
removed. The sample should be ground with a mortar and pestle and passed through a 60-
mesh sieve. Only the coarse rock fraction should remain on the screen.
7.2.3 The sample should be homogenized by using a riffle splitter or by placing 150
to 200 grams of the dried, sieved sample on a piece of kraft or butcher paper about 1.5 by 1.5
feet in size. Each corner of the paper should be lifted alternately, rolling the soil over on itself
and toward the opposite corner. The soil should be rolled on itself 20 times. Approximately
5 grams of the sample should then be removed and placed in a sample cup for FPXRF
analysis. The rest of the prepared sample should be sent off site for ICP or AA analysis. The
method use for confirmatory analysis should meet the data quality objectives of the project.
7 .3 Blank Samples: The blank samples should be from a "clean" quartz or silicon dioxide
matrix that is free of any analytes at concentrations above the method detection limits. These
samples are used to monitor for cross-contamination and laboratory-induced contaminants or
interferences. ·
7.4 Standard Reference Materials: Standard reference materials (SRM) are standards
containing certified amounts of metals in soil or sediment. These standards are used for accuracy
and performance checks of FPXRF analyses. SRMs can be obtained from the National Institute
of Standards and Technology (NIST), the U.S. Geological Survey (USGS), the Canadian National
Research Council, and the national bureau of standards in foreign nations. Pertinent NIST SRMs
for FPXRF analysis include 2704, Buffalo River Sediment; 2709, San Joaquin Soil; and 2710 and
2711, Montana Soil. These SRMs contain soil or sediment from actual sites that has been
analyzed using independent inorganic analytical methods by many different laboratories.
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE
Sample handling and preservation procedures used in FPXRF analyses should follow the
guidelines in Chapter Three, Inorganic Analytes.
9.0 QUALITY CONTROL
9.1 Refer to Chapter One for additional guidance on quality assurance protocols. All field
data sheets and quality control data should be maintained for reference or inspection.
9.2 Energy Calibration Check: To determine whether an FPXRF instrument is operating
within resolution and stability tolerances, an energy calibration check should be run. The energy
calibration check determines whether the characteristic x-ray lines are shifting, which would indicate
drift within the instrument. As discussed in Section 4.10, this check also serves as a gain check
in the event that ambient temperatures are fluctuating greatly(> 10 to 20'F).
The energy calibration check should be run at a frequency consistent with manufacturers
recommendations. Generally, this would be at the beginning of each working day, after the
batteries are changed or the instrument is shut off, at the end of each working day, and at any other
time when the instrument operator believes that drift is occurring during analysis. A pure element
such as iron, manganese, copper, or lead is often used for the energy calibration check. A
manufacturer-recommended count time per source should be used for the check.
9.2.1 -The i_nstrument manufacturer's manual specifies the channel or kiloelectron
volt level at which a pure element peak should appear and the expected intensity of the peak.
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The intensity and channel number of the pure element as measured using the radioactive
source should be checked and compared to the manufacturer's recommendation. If the
energy calibration check does not meet the manufacturer's criteria, then the pure element
sample should be repositioned and reanalyzed. If the criteria are still not met, then an energy
calibration should be performed as described in the manufacturer's manual. With some
FPXRF instruments, once a spectrum is acquired from the energy calibration check, the peak
can be optimized and realigned to the manufacturer's specifications using their software.
9.3 Blank Samples: Two types of blank samples should be analyzed for FPXRF analysis:
instrument blanks and method blanks. An instrument blank is used to verify that no contamination
exists in the spectrometer or on the probe window.
9.3.1 The instrument blank can be silicon dioxide, a Teflon block, a quartz block,
"clean" sand, or lithium carbonate. This instrument blank should be analyzed on each
working day before and after analyses are conducted and once per every twenty" samples.
An instrument blank should also be analyzed whenever contamination is suspected by the
analyst. The frequency of analysis will vary with the data quality objectives of the project. A
manufacturer-recommended count time per source should be used for the blank analysis.
No element concentrations above the method detection limits should be found in the
instrument blank. If concentrations exceed these limits, then the probe window and the check
sample should be checked for contamination. If contamination is not a problem, then the
instrument must be "zeroed" by following the manufacturer's instructions.
9.3.2 A method blank is used to monitor for laboratory-induced contaminants or
interferences. The method blank can be "clean" silica sand or lithium carbonate that
undergoes the same preparation procedure as the samples. A method blank must be
analyzed at least daily. The frequency of analysis will depend on the data quality objectives
of the project. To be acceptable, a method blank must not contain any analyte at a
concentration above its method detection limit. If an analyte's concentration exceeds its
method detection limit, the cause of the problem must be identified, and all samples analyzed
with the method blank must be reanalyzed.
9.4 Calibration Verification Checks: A calibration verification check sample is used to
check the accuracy of the instrument and to assess the stability and consistency of the analysis for
the analytes of interest. A check sample should be analyzed at the beginning of each working day,
during active sample analyses, and at the end of each working day. The frequency of calibration
checks during active analysis will depend on the data quality objectives of the project. The check
sample should be a well characterized soil sample from the site that is representative of site
samples in terms of particle size and degree of homogeneity and that contains contaminants at
concentrations near the action levels. If a site-specific sample is not available, then an NIST or
other SRM that contains the analytes of interest can be used to verify the accuracy of the
instrument. The measured value for each target analyte should be within ±20 percent (%0) of the
true value for the calibration verification check to be acceptable. If a measured value falls outside
this range, then the check sample should be reanalyzed. If the value continues to fall outside the
acceptance range, the instrument should be recalibrated, and the batch of samples analyzed before
the unacceptable calibration verification check must be reanalyzed.
9.5 Precision Measurements: The precision of the method is monitored by analyzing a
sample with low, moderate, or high concentrations of target analytes. The frequency of precision
measurements will depend on the data quality objectives for the data. A minimum of one precision
sample should be run per day. Each precision sample should be analyzed 7 times in replicate. It
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is recommended that precision measurements be obtained for samples with varying concentration
ranges to assess the effect of concentration on method precision. Determining method precision
for analytes at concentrations near the site action levels can be extremely important if the FPXRF
results are to be used in an enforcement action; therefore, selection of at least one sample with
target analyte concentrations at or near the site action levels or levels of concern is recommended.
A precision sample is analyzed by the instrument for the same field analysis time as used for other
project samples. The relative standard deviation (RSD) of the sample mean is used to assess
method precision. For FPXRF data to be considered adequately precise, the RSD should not be
greater than 20 percent with the exception of chromium. RSD values for chromium should not be
greater than 30 percent.
The equation for calculating RSD is as follows:
RSD = (SD/Mean Concentration) x 100
where:
RSD =
SD =
Mean Concentration =
Relative standard deviation for the rrecision measurement for
the analyte
Standard deviation of the concentration for the analyte
Mean concentration for the analyte
The precision or reproducibility of a measurement will improve with increasing count time,
however, increasing the count time by a factor of 4 will provide only 2 times better precision, so
there is a point of diminishing return. Increasing the count time also improves the detection limit,
but decreases sample throughput.
9.6 Detection Limits: Results for replicate analyses of a low-concentration sample, SSCS,
or SRM can be used to generate an average site-specific method detection and quantitation limits.
In this case, the method detection limit is defined as 3 times the standard deviation of the results
for the low-concentration samples and the method quantitation limit is defined as 10 times the
standard deviation of the same results. Another means of determining method detection and
quantitation limits involves use of counting statistics. In FPXRF analysis, the standard deviation
from counting statistics is defined as SD = (N)Y., where SD is the standard deviation for a target
analyte peak and N is the net counts for the peak of the analyte of interest (i.e., gross counts minus
background under the peak). Three times this standard deviation would be the method detection
limit and 10 times this standard deviation would be the method quantitation limit. If both of the
above mentioned approaches are used to calculate method detection limits, the larger of the
standard deviations should be used to provide the more conservative detection limits.
This SD based detection limit criteria must be used by the operator to evaluate each
measurement for its useability. A measurement above the average calculated or manufacturer's
detection limit, but smaller than three times its associated SD, should not be used as a quantitative
measurement. Conversely, if the measurement is below the average calculated or manufacturer's
detection limit, but greater than three times its associated SD. It should be coded as an estimated
value.
9. 7 Confirmatory Samples: The comparability of the FPXRF analysis is determined by
submitting FPXRF-analyzed samples for analysis at a laboratory. The method of confirmatory
analysis must meet the project and XRF measurement data quality objectives. The confirmatory
samples must be splits of the well homogenized sample material. In some cases the prepared
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sample cups can be submitted. A minimum of 1 sample for each 20 FPXRF-analyzed samples
should be submitted for confirmatory analysis. This frequency will depend on data quality
objectives. The confirmatory analyses can also be used to verify the quality of the FPXRF data.
The confirmatory samples should be selected from the lower, middle, and upper range of
concentrations measured by the FPXRF. They should also include samples with analyte
concentrations at or near the site action levels. The results of the confirmatory analysis and FPXRF
analyses should be evaluated with a least squares linear regression analysis. If the measured
concentrations span more than one order of magnitude, the data should be log-transformed to
standardize variance which is proportional to the magnitude of measurement. The correlation
coefficient {r) for the results should be 0. 7 or greater for the FPXRF data to be considered
screening level data. If the r2 is 0.9 or greater and inferential statistics indicate the FPXRF data and
the confirmatory data are statistically equivalent at a 99 percent confidence level, the data could
potentially meet definitive level data criteria.
10.0 CALIBRATION AND STANDARDIZATION
10.1 Instrument Calibration: Instrument calibration procedures vary among FPXRF
instruments. Users of this method should follow the calibration procedures outlined in the
operator's manual for each specific FPXRF instrument. Generally, however, three types of
calibration procedures exist for FPXRF instruments: FP calibration, empirical calibration, and the
Compton peak ratio or normalization !11ethod. These three types of calibration are discussed below.
10.2 Fundamental Parameters Calibration: FP calibration procedures are extremely
variable. An FP calibration provides the analyst with a "standardless" calibration. The advantages
of FP calibrations over empirical calibrations include the following:
No previously collected site-specific samples are required, although
site-specific samples with confirmed and validated analytical results for all
elements present could be used.
Cost is reduced because fewer confirmatory laboratory results_ or
calibration standards are required.
However, the analyst should be aware of the limitations imposed on FP calibration by particle
size and matrix effects. These limitations can be minimized by adhering to the preparation
procedure described in Section 7 .2. The two FP calibration processes discussed below are based
on an effective energy FP routine and a back scatter with FP (BFP) routine. Each FPXRF FP
calibration process is based on a different iterative algorithmic method. The calibration procedure
for each routine is explained in detail in the manufacturer's user manual for each FPXRF
instrument; in addition, training courses are offered for each instrument.
10.2.1 Effective Energy FP Calibration: The effective energy FP calibration is
performed by the manufacturer before an instrument is sent to the analyst. Although SSCS
can be used, the calibration relies on pure element standards or SRMs such as those
obtained from NIST for the FP calibration. The effective energy routine relies on the
spectrometer response to pure elements and FP iterative algorithms to compensate for
various matrix effects.
Alpha coefficients are calculated using a variation of the Sherman equation, which
calculates theoretical intensities from the measurement of pure element samples. These
coefficients indicate the quantitative effect of each matrix element on an analyte's measured
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x-ray intensity. Next, the Lachance Traill algorithm is solved as a set of simultaneous
equations based on the theoretical intensities. The alpha coefficients are then downloaded
into the specific instrument.
The working effective energy FP calibration curve must be verified before sample
analysis begins on each working day, after every 20 samples are analyzed, and at the end
of sampling. This verification is performed by analyzing either an NIST SRM or an SSCS that
is representative of the site-specific samples. This SRM or SSCS serves as a calibration
check. A manufacturer-recommended count time per source should be used for the
calibration check. The analyst must then adjust the y-intercept and slope of the calibration
curve to best fit the known concentrations of target analytes in the SRM or SSCS.
A percent difference (%D) is then calculated for each target analyte. The %D should
be within ±20 percent of the certified value for each analyte. If the %D falls outside this
acceptance range, then the calibration curve should be adjusted by varying the slope of the
line or the y-intercept value for the analyte. The SRM or SSCS is reanalyzed until the %D
falls within ±20 percent. The group of 20 samples analyzed before an out-of-control
calibration check should be reanalyzed.
The equation to calibrate %D is as follows:
%D = ((C, -C,) IC,) x 100
where:
%D = Percent difference
C, = Certified concentration of standard sample
C, = Measured concentration of standard sample
10.2.2 BFP Calibration: BFP calibration relies on the ability of the liquid nitrogen-
cooled, Si(Li) solid-state detector to separate the coherent (Compton) and incoherent
(Rayleigh) backscatter peaks of primary radiation. These peak intensities are known to be
a function of sample composition, and the ratio of the Compton to Rayleigh peak is a function
of the mass absorption of the sample. The calibration procedure is explained in detail in the
instrument manufacturer's manual. Following is a general description of the BFP calibration
procedure.
The concentrations of all detected and quantified elements are entered into the
computer software system. Certified element results for an NIST SRM or confirmed and
validated results for an SSCS can be used. In addition, the concentrations of oxygen and
silicon must be entered; these two concentrations are not found in standard metals analyses.
The manufacturer provides silicon and oxygen concentrations for typical soil types. Pure
element standards are then analyzed using a manufacturer-recommended count time per
source. The results are used to calculate correction factors in order to adjust for spectrum
overlap of elements.
The working BFP calibration curve must be verified before sample analysis begins on
each working day, after every 20 samples are analyzed, and at the end of the analysis. This
verification is performed by analyzing either an NIST SRM or an SSCS that is representative
of the site-specific samples. This SRM or SSCS serves as a calibration check. The standard
sample is analyzed using a manufacturer-recommended count time per source to check the
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calibration curve. The analyst must then adjust the y-intercept and slope of the calibration
curve to best fit the known concentrations of target analytes in the SRM or SSCS.
A %D is then calculated for each target analyte. The %D should fall within ±20
percent of the certified value for each analyte. If the %D falls outside this acceptance range,
then the calibration curve should be adjusted by varying the slope of the line they-intercept
value for the analyte. The standard sample is reanalyzed until the %D falls within ±20 percent.
The group of 20 samples analyzed before an out-of-control calibration check should be
reanalyzed.
10.3 Empirical Calibration: An empirical calibration can be performed with SSCS, site-
typical standards, or standards prepared from metal oxides. A discussion of SSCS is included in
Section 7.2; if no previously characterized samples exist for a specific site, site-typical standards
can be used. Site-typical standards may be selected from commercially available characterized
soils or from SSCS prepared for another site. The site-typical standards should closely
approximate the site's soil matrix with respect to particle size distribution, mineralogy, and
contaminant analytes. If neither SSCS nor site-typical standards are available, it is possible to
make gravimetric standards by adding metal oxides to a "clean" sand or silicon dioxide matrix that
simulates soil. Metal oxides can be purchased from various chemical vendors. If standards are
made on site, a balance capable of weighing items to at least two decimal places is required.
Concentrated ICP or AA standard solutions can also be used to make standards. These solutions
are available in concentrations of 10,000 parts per million, thus only small volumes have to be
added to the soil.
An empirical calibration using SSCS involves analysis of SSCS by the FPXRF instrument and
by a conventional analytical method such as ICP or AA. A total acid digestion procedure should
be used by the laboratory for sample preparation. Generally, a minimum of 10 and a maximum of
30 well characterized SSCS, site-typical standards, or prepared metal oxide standards are required
to perform an adequate empirical calibration. The number of required standards depends on the
number of analytes of interest and interfering elements. Theoretically, an empirical calibration with
SSCS should provide the most accurate data for a site because the calibration compensates for
site-specific matrix effects.
The first step in an empirical calibration is to analyze the pure element standards for the
elements of interest. This enables the instrument to set channel limits for each element for spectral
deconvolution. Next the SSCS, site-typical standards, or prepared metal oxide standards are
analyzed using a count time of 200 seconds per source or a count time recommended by the
manufacturer. This will produce a spectrum and net intensity of each analyte in each standard.
The analyte concentrations for each standard are then entered into the instrument software; these
concentrations are those obtained from the laboratory, the certified results,-or the gravimetrically
determined concentrations of the prepared standards. This gives the instrument analyte values to
regress against corresponding intensities during the modeling stage. The regression equation
correlates the concentrations of an analyte with its net intensity.
The calibration equation is developed_ using a least squares fit regression analysis. After the
regression terms to be used in the equation are defined, a mathematical equation can be developed
to calculate the analyte concentration in an unknown sample. In some FPXRF instruments, the
software of the instrument calculates the regression equation. The software uses calculated
intercept and slope values to form a multiterm equation. In conjunction with the software in the
instrument, the operator can adjust the multiterm equation to minimize interelement interferences
and optimize the intensity calibration curve.
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It is possible to define up to six linear or nonlinear terms in the regression equation. Terms
can be added and deleted to optimize the equation. The goal is to produce an equation with the
smallest regression error and the highest correlation coefficient. These values are automatically
computed by the software as the regression terms are added, deleted, or modified. It is also
possible to delete data points from the regression line if these points are significant outliers or if
they are heavily weighing the data. Once the regression equation has been selected for an analyte,
the equation can be entered into the software for quantitation of analytes in subsequent samples.
For an empirical calibration to be acceptable, the regression equation for a specific analyte should
have a correlation coefficient of 0.98 or greater or meet the DQOs of the project.
In an empirical calibration, one must apply the DQOs of the project and ascertain critical or
action levels for the analytes of interest. It is within these concentration ranges or around these
action levels that the FPXRF instrument should be calibrated most accurately. It may not be
possible to develop a good regression equation over several orders of analyte concentration.
10.4 Compton Normalization Method: The Compton normalization method is based on
analysis of a single, certified standard and normalization for the Compton peak. The Compton peak
is produced from incoherent backscattering of x-ray radiation from the excitation source and is
present in the spectrum of every sample. The Compton peak intensity changes with differing
matrices. Generally, matrices dominated by lighter elements produce a larger Compton peak, and
those dominated by l1eavier elements produce a smaller Compton peak. Normalizing to the
Compton peak can reduce problems with varying matrix effects among samples. Compton
normalization is similar to the use of internal standards in organics analysis. The Compton
normalization method may not be effective when analyte concentrations exceed a few percent.
The certified standard used for this type of calibration could be an NIST SRM such as 271 0
or 2711. The SRM must be a matrix similar to the samples and must contain the analytes of
interests at concentrations near those expected in the samples. First, a response factor has to be
determined for each analyte. This factor is calculated by dividing the net peak intensity by the
analyte concentration. The net peak intensity is gross intensity corrected for baseline interference.
Concentrations of analytes in samples are then determined by multiplying the baseline corrected
analyte signal intensity by the normalization factor and by the response factor. The normalization
factor is the quotient of the baseline corrected Compton K0 peak intensity of the SRM divided by
that of the samples. Depending on the FPXRF instrument used, these calculations may be done
manually or by the instrument software.
11.0 PROCEDURE
1 f.1 Operation of the various FPXRF instruments will vary according to the manufacturers'
protocols. Before operating any FPXRF instrument, one should consult the manufacturer's manual.
Most manufacturers recommend that their instruments be allowed to warm up for 15 to 30 minutes
before analysis of samples. This will help alleviate drift or energy calibration problems later on in
analysis.
11.2 Each FPXRF instrument should be operated according to the manufacturer's
recommendations. There are two modes in which FPXRF instruments can be operated: in situ and
intrusive. The in situ mode involves analysis of an undisturbed soil sediment or sample. Intrusive
analysis involves collection and preparation of a soil or sediment sample before analysis. Some
FPXRF instruments can operate in both modes of analysis, while others are designed to operate
in only one mode. The two modes of analysis are discussed below.
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11.3 For in situ analysis, one requirement is that any large or non representative debris be
removed from the soil surface before analysis. This debris includes rocks, pebbles, leaves,
vegetation, roots, and concrete. Another requirement is that the soil surface be as smooth as
possible so that the probe window will have good contact with the surface. This may require some
leveling of the surface with a stainless-steel trowel. During the study conducted to provide data for
this method, this modest amount of sample preparation was found to take less than 5 minutes per
sample location. The last requirement is that the soil or sediment not be saturated with water.
Manufacturers state that their FPXRF instruments will perform adequately for soils with moisture
contents of 5 to 20 percent but will not perform well for saturated soils, especially if ponded water
exists on the surface. Another recommended technique for in situ analysis is to tamp the soil to
increase soil density and compactness for better repeatability and representativeness. This
condition is especially important for heavy element analysis, such as barium. Source count times
for in situ analysis usually range from 30 to 120 seconds, but source count times will vary among
instruments and depending on required detection limits.
11 .4 For intrusive analysis of surface or sediment, it is recommended that a sample be
collected from a 4-by 4-inch square that is 1 inch deep. This will produce a soil sample of
approximately 375 grams or 250 cm 3, which is enough soil to fill an 8-ounce jar. The sample shoulcl
be homogenized, dried, and ground before analysis. The sample can be homogenized before or
after drying. The homogenization technique to be used after drying is discussed in Section 4.2.
If the sample is homogenized before drying, it should be thoroughly mixed in a beaker or similar
container, or if the sample is moist and has a high clay content, it can be kneaded in a plastic bag.
One way to monitor homogenization when the sample is kneaded in a plastic bag is to add sodium
fluorescein dye to the sample. After the moist sample has been homogenized, it is examined under
an ultraviolet light to assess the distribution of sodium fluorescein throughout the sample. If the
fluorescent dye is evenly distributed in the sample, homogenization is considered complete; if the
dye is not evenly distributed, mixing should continue until the sarnpie has been thoroughiy
homogenized. During the study conducted to provide data for this method, the homogenization
procedure using the fluorescein dye required 3 to 5 minutes per sample. As demonstrated in
Sections 13.5 and 13.7, homogenization has the greatest impact on the reduction of sampling
variability. It produces little or no contamination. Often, ii can be used without the more labor
intensive steps of drying, grinding, and sieving given in Sections 11.5 and 11.6. Of course, to
achieve the best data quality possible all four steps must be followed.
11.5 Once the soil or sediment sample has been homogenized, it should be dried. This can
be accomplished with a toaster oven or convection oven. A small aliquot of the sample (20 to 50
grams) is placed in a suitable container for drying. The sample should be dried for 2 to 4 hours in
the convection or toaster oven at a temperature not greater than 150°C. Microwave drying is not
a recommended procedure. Field studies have shown that microwave drying can increase
variability between the FPXRF data and confirmatory analysis. High levels of metals in a sample
can cause arcing in the microwave oven, and sometimes slag forms in the sample. Microwave
oven drying can also melt plastic containers used to hold the sample.
11.6 The homogenized dried sample material should be ground with a mortar and pestle
and passed through a 60-mesh sieve to achieve a uniform particle size. Sample grinding should
continue until at least 90 percent of the original sample passes through the sieve. The grinding step
normally takes an average of 1 O minutes per sample. An aliquot of the sieved sample should then
be placed in a 31.0-mm polyethylene sample cup (or equivalent) for analysis. The sample cup
should be one-half to three-quarters full at a minimum. The sample cup should be covered with a
2.5 µm Mylar (or equivalent) film for analysis. The rest of the soil sample should be placed in a jar,
labeled, and archived for possible confirmation analysis. All equipment including the mortar, pestle,
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and sieves must be thoroughly cleaned so that any cross-contamination is below the MDLs of the
procedure or DQOs of the analysis.
12.0 DA TA ANALYSIS AND CALCULATIONS
Most FPXRF instruments have software capable of storing all analytical results and spectra. The
results are displayed in parts per million and can be downloaded to a PC, which can provide a hard
copy printout. Individual measurements that are smaller than three times their associated SD
should not be used for quantitation.
13.0 METHOD PERFORMANCE
13.1 This section discusses four performance factors, field-based method detection limits,
precision, accuracy, and comparability to EPA-approved methods. The numbers presented in
Tables 4 through 9 were generated from data obtained from six FPXRF instruments. The soil
samples analyzed by the six FPXRF instruments were collected from two sites in the United States.
The soil samples contained several of the target analytes at concentrations ranging from non detect
to tens of thousands of mg/kg.
13.2 The six FPXRF instruments included the TN 9000 and TN Lead Analyzer
manufactured by TN Spectrace; the X-MET 920 with a Sili detector and X-MET 920 with a gas-
filled proportional detector manufactured by Metorex, Inc.; the XL Spectrum Analyzer manufactured
by Niton; and the MAP Spectrum Analyzer manufactured by Scitec. The TN 9000 and TN Lead
Analyzer both have a Hgl2 detector. The TN 9000 utilized an Fe-55, Cd-109, and Am-241 source.
The TN Lead Analyzer had only a Cd-109 source. The X-Met 920 with the Sili detector had a Cd-
109 and Am-241 source. The X-MET 920 with the gas-filled proportional detector had only a Cd-
109 source. The XL Spectrum A:1alyzer utilized a silicon pin-dio<..!e detector and a Cd-109 source.
The MAP Spectrum Analyzer utilized a solid-state silicon detector and a Cd-109 source.
13.3 All data presented in Tables 4 through 9 were generated using the following
calibrations and source count times. The TN 9000 and TN Lead Analyzer were calibrated using
fundamental parameters using NIST SRM 2710 as a calibration check sample. The TN 9000 was
operated using 100, 60, and 60 second count times for the Cd-109, Fe-55, and Am-241 sources,
respectively. The TN Lead analyzer was operated using a 60 second count time for the Cd-109
source. The X-MET 920 with the Si(Li) detector was calibrated using fundamental parameters and
one well characterized site-specific soil standard as a calibration check. It used 140 and 100
second count times for the Cd-109 and Am-241 sources, respectively. The X-MET 920 with the
gas-filled proportional detector was calibrated empirically using between 10 and 20 well
characterized site-specific soil standards. It used 120 second times for the Cd-109 source. The
XL Spectrum Analyzer utilized NIST SRM 2710 for calibration and the Compton peak normalization
procedure for quantitation based on 60 second count times for the Cd-109 source. The MAP
Spectrum Analyzer was internally calibrated by the manufacturer. The calibration was checked
using a well-characterized site-specific soil standard. It used 240 second times for the Cd-109
source.
13.4 Field-Based Method Detection Limits: The field-based method detection limits are
presented in Table 4. The field-based method detection limits were determined by collecting ten
replicate measurements on site-specific soil samples with metals concentrations 2 to 5 times the
expected method detection limits. Based on these ten replicate measurements, a standard
deviation on the.replicate analysis was calculated. The method detection limits presented in Table
4 are defined as 3 times the standard deviation for each analyte. ·
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The field-based method detection limits were generated by using the count times discussed
earlier in this section. All the field-based method detection limits were calculated for soil samples
that had been dried and ground and placed in a sample cup with the exception of the MAP
Spectrum Analyzer. This instrument can only be operated in the in situ mode, meaning the samples
were moist and not ground.
Some of the analytes such as cadmium, mercury, silver, selenium, and thorium were not
detected or only detected at very low concentrations such that a field-based method detection limit
could not be determined. These analytes are not presented in Table 4. Other analytes such as
calcium, iron, potassium, and titanium were only found at high concentrations (thousands of mg/kg)
so that reasonable method detection limits could not be calculated. These analytes also are not
presented in Table 4.
13.5 Precision Measurements: The precision data is presented in Table 5. Each of the six
FPXRF instruments performed 10 replicate measurements on 12 soil samples that had analyte
concentrations ranging from nondetects to thousands of mg/kg. Each of the 12 soil samples
underwent 4 different preparation techniques from in situ (no preparation) to dried and ground in
a sample cup. Therefore, there were 48 precision data points for five of the instruments and 24
precision points for the MAP Spectrum Analyzer. The replicate measurements were taken using
the source count times discussed at the beginning of this section.
For each detectable analyte in each precision sample a mean concentration, standard
deviation, and RSD was calculated for each analyte. The data presented in Table 5 is an average
RSD for the precision samples that had analyte concentrations at 5 to 10 times the MDL for that
analyte for each instrument. Some analytes such as mercury, selenium, silver, and thorium were
not detected in any of the precision samples so these analytes are not listed in Table 5. Some
analytes such as cadmium. nickel, and lin were only detected at concentrations near the MDLs so
that an RSD value calculated at 5 to 10 times the MDL was not possible.
One FPXRF instrument collected replicate measurements on an additional nine soil samples
to provide a better assessment of the effect of sample preparation on precision. Table 6 shows
these results. The additional nine soil samples were comprised of three from each texture and had
analyte concentrations ranging from near the detection limit of the FPXRF analyzer to thousands
of mg/kg. The FPXRF analyzer only collected replicate measurements from three of the
preparation methods; no measurements were collected from the in situ homogenized samples. The
FPXRF analyzer conducted five replicate measurements of the in situ field samples by taking
measurements at five different points within the 4-inch by 4-inch sample square. Ten replicate
measurements were collected for both the intrusive undried and unground and intrusive dried and
ground samples contained in cups. The cups were shaken between each replicate measurement.
Table 6 shows that the precision dramatically improved from the in situ to the intrusive
measurements. In general there was a slight improvement in precision when the sample was dried
and ground. Two factors caused the precision for the in situ measurements to be poorer. The
major factor is soil heterogeneity. By moving the probe within the 4-inch by 4-inch square,
measurements of different soil samples were actually taking place within the square. Table 6
illustrates the dominant effect of soil heterogeneity. It overwhelmed instrument precision when the
FPXRF analyzer was used in this mode. The second factor that caused the RSD values to be
higher for the in situ measurements is the fact that only five versus ten replicates were taken. A
lesser number of measurements caused the standard deviation to be larger which in turn elevated
the RSD values.
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13.6 Accuracy Measurements: Five of the FPXRF instruments (not including the MAP
Spectrum Analyzer) analyzed 18 SRMs using the source count times and calibration methods given
at the beginning of this section. The 18 SRMs included 9 soil SRMs, 4 stream·or river sediment
SR Ms, 2 sludge SRMs, and 3 ash SRMs. Each of the SRMs contained known concentrations of
certain target analytes. A percent recovery was calculated for each analy1e in each SRM for each
FPXRF instrument. Table 7 presents a summary of this data. With the exception of cadmium,
chromium, and nickel, the values presented in Table 7 were generated from the 13 soil and
sediment SRMs only. The 2 sludge and 3 ash SRMs were included for cadmium, chromium, and
nickel because of the low or nondetectable concentrations of these three analytes in the soil and
sediment SRMs.
Only 12 analytes are presented in Table 7. These are the analy1es that are of environmental
concern and provided a significant number of detections in the SR Ms for an accuracy assessment.
No data is presented for the X-MET 920 with the gas-filled proportional detector. This FPXRF
instrument was calibrated empirically using site-specific soil samples. The percent recovery values
from this instrument were very sporadic and the data did not lend itself to presentation in Table 7.
Table 8 provides a more detailed summary of accuracy data for one FPXRF instrument (TN
9000) for the 9 soil SRMs and 4 sediment SRMs. Table 8 shows the certified value, measured
value, and percent recovery for five analytes. These analytes were chosen because they are of
environmental concern and were most prevalently certified for in the SRM and detected by the
FPXRF instrument. The first nine SRMs are soil and the last 4 SRMs are sediment. Percent
recoveries for the four N 1ST SR Ms were often between 90 and 110 percent for all analytes.
13.7 Comparability: Comparability refers to the confidence with which one data set can be
compared to another. In this case, FPXRF data generated from a large study of six FPXRF
instruments was compared to SW-846 Methods 3050 and 6010 which are the stc1nclard soil
extraction for metals and analysis by inductively coupled plasma. An evaluation of comparability
was conducted by using linear regression analysis. Three factors were determined using the linear
regression. These factors were the y-intercept, the slope of the line, and the coefficient of
determination (r).
As part of the comparability assessment, the effects of soil type and preparation methods
were studied. Three soil types (textures) and four preparation methods were examined during the
study. The preparation methods evaluated the cumulative effect of particle size, moisture, and
homogenization on comparability. Due to the large volume of data produced during this study,
linear regression data for six analytes from only one FPXRF instrument is presented in Table 9.
Similar trends in the data were seen for all instruments.
Tabl_e 9 shows the regression parameters for the whole data set, broken out by soil type, and
by preparation method. The soil types are as follows: soil 1--sand; soil 2--loam; and soil 3--silty
clay. The preparation methods are as follows: preparation 1--in situ in the field; preparation 2--in
situ, sample collected and homogenized; preparation 3--intrusive, with sample in a sample cup but
sample still wet and not ground; and preparation 4--sample dried, ground, passed through a 40-
mesh sieve, and placed in sample cup.
For arsenic, copper, lead, and zinc, the comparability to the confirmatory laboratory was
excellent with r2 values ranging from 0.80 to 0.99 for all six FPXRF instruments. The slopes of the
regression lines for arsenic, copper, lead, and zinc, were generally between 0.90 and 1.00
indicating the data would need to be corrected very little or not at all to match the confirmatory
laboratory data. The r2 values and slopes of the regression lines for barium and chromium were
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not as good as for the other for analytes, indicating the data would have to be corrected to match
the confirmatory laboratory.
Table 9 demonstrates that there was little effect of soil type on the regression parameters for
any of the six analytes. The only exceptions were for barium in soil 1 and copper in soil 3. In both
of these cases, however, it is actually a concentration effect and not a soil effect causing the poorer
comparability. All barium and copper concentrations in soil 1 and 3, respectively, were less than
350 mg/kg.
Table 9 shows there was a preparation effect on the regression parameters for all six
analytes. With the exception of chromium, the regression parameters were primarily improved
going from preparation 1 to preparation 2. In this step, the sample was removed from the soil
surface, all large debris was removed, and the sample was thoroughly homogenized. The
additional two preparation methods did little to improve the regression parameters. This data
indicates that homogenization is the most critical factor when comparing the results. It is essential
that the sample sent to the confirmatory laboratory match the FPXRF sample as closely as
possible.
Section 11.0 of this method discusses the time necessary for each of the sample preparation
techniques. Based on the data quality objectives for the project, an analyst must decide if it is worth
the extra time required to dry and grind the sample for small improvements in comparability.
Homogenization requires 3 to 5 minutes. Drying the sample requires one to two hours. Grinding
and sieving requires another 10 to 15 minutes per sample. Lastly, when grinding and sieving is
conducted, time must be allotted to decontaminate the mortars, pestles, and sieves. Drying and
grinding the samples and decontamination procedures will often dictate that an extra person be on
site so that the analyst can keep up with the sample collection crew. The cost of requiring an extra
person on site to prepare samples must be balanced with the gain in data quality and sample
throughput. ·
13.8 The following documents may provide additional guidance and insight on this method
and technique:
13.8.1 Hewitt, A.O. 1994. "Screening for Metals by X-ray Fluorescence
Spectrometry/Response Factor/Compton K, Peak Normalization Analysis." American
Environmental Laboratory. Pages.24-32.
13.8.2 Piorek, S., and J.R. Pasmore. 1993. "Standardless, In Situ Analysis of
Metallic Contaminants in the Natural Environment With a PC-Based, High Resolution Portable
X-Ray Analyzer." Third International Symposium on Field Screening Methods for Hazardous
Waste and Toxic Chemicals. Las Vegas, Nevada. February 24-26, 1993. Volume 2, Pages
1135-1151.
14.0 POLLUTION PREVENTION
14.1 Pollution prevention encompasses any technique that reduces or eliminates the
quantity and/or toxicity of waste at the point of generation. Numerous opportunities for pollution
prevention exist in laboratory operation. The EPA has established a preferred hierarchy of
environmental management techniques that places pollution prevention as the management option
offirst choice. Whenever feasible, laboratory personnel should use pollution prevention techniques
to address their waste generation. When wastes cannot be feasibly reduced at the source, the
Agency recommends recycling as the next best option.
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14.2 For information about pollution prevention that may be applicable to laboratories and
research institutions consult Less is Better: Laboratory Chemical management for Waste Reduction
available from the American Chemical Society's Department of Government Relations and Science
Policy, 1155 16th Street N.W., Washington D.C. 20036, [phone].
15.0 WASTE MANAGEMENT
The Environmental Protection Agency requires that laboratory waste management practices
be conducted consistent with all applicable rules and regulations. The Agency urges laboratories
to protect the air, water, and land by minimizing and controlling all releases from hoods and bench
operations, complying with the letter and spirit of any sewer discharge permits and regulations, and
by complying with all solid and hazardous waste regulations, particularly the hazardous waste
identification rules and land disposal restrictions. For further information on waste management,
consult The Waste Management Manual for Laboratory Personnel available from the American
Chemical Society at the address listed in Sec. 14.2.
16.0 REFERENCES
1. Metorex. X-MET 920 User's Manual.
2. Spectrace Instruments. 1994. Energy Dispersive X-ray Fluorescence Spectrometry: An
Introduction.
3. TN Spectrace. Spectrace 9000 Field Portable/Benchtop XRF Training and Applications .
Manual.
4. Unpublished SITE data, recieved from PRC Environment Management, Inc.
17.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA
The pages to follow contain Tables 1 through 9 and a method procedure flow diagram.
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CD-ROM
TABLE 1
INTERFERENCE FREE DETECTION LIMITS
Analyte Chemical
Abstract
Series Number
Antimony (Sb) 7440-36-0
Arsenic (As). 7440-38-0
Barium (Ba) 7440-39-3
Cadmium (Cd) 7440-43-9
Calcium (Ca) 7440-70-2
Chromium (Cr) 7440-47-3
Cobalt (Co) 7440-48-4
Copper (Cu) 7440.-50-8
Iron (Fe) 7439-89-6
Lead (Pb) 7439-92-1
Manganese (Mn) 7439-96-5
Mercury (Hg) 7439-97-6
Molybdenum (Mo) 7439-93-7
Nickel (Ni) 7440-02-0
Potassium (K) 7440-09-7
Rubidium (Rb) 7440-17-7
Selenium (Se) 7782-49-2
Silver (Ag) 7440-22-4
Strontium (Sr) 7440-24-6
Thallium (Tl) 7440-28-0
Tho.rium (Th) 7440-29-1
Tin (Sn) 7440-31-5
Titanium (Ti) 7440-32-6
Vanadium (V) 7440-62-2
Zinc (Zn) 7440-66-6
Zirconium (Zr) 7440-67-7
Source: References 1, 2, and 3
6200 -23
Detection Limit in
Quartz Sand
(milligrams per kilogram)
40
40
20
100
70
150
60
50
60
20
70
30
10
50
200
10
40
70
10
20
10
60
50
50
50
10
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TABLE 2
SUMMARY OF RADIOISOTOPE SOURCE CHARACTERISTICS
Source Activity Half-Life Excitation Energy Elemental Analysis Range
fmCi\ (Years) lkeV)
Fe-55 20-50 2.7 5.9 Sulfur to Chromium K Lines
Molybdenum to Barium L Lines
Cd-109 5-30 1.3 22.1 and 87.9 Calcium to Rhodium K Lines
Tantalum to Lead K Lines
Barium to Uranium L Lines
Am-241 5-30 458 26.4 and 59.6 Copper to Thulium K Lines
Tunasten to Uranium L Lines
Cm-244 60-100 17.8 14.2 Titanium to Selenium K Lines
Lanthanum to Lead L Lines
Source: Reference 1, 2, and 3
TABLE 3
SUMMARY OF X-RAY TUBE SOURCE CHARACTERISTICS
Anode Recommended K-alpha Elemental /,nalysis Range
Material Voltage Range Emission
/kV) /keV)
Cu 18-22 8.04 Potassium to Cobalt K Lines
Silver to Gadolinium L Lines
Mo 40-50 17.4 Cobalt to Yttrium K Lines
Eurooium to Radon L Lines
Ag 50-65 22.1 Zinc to Technicium K Lines
Ytterbium to Neotunium L Lines
Source: Reference 4
Notes: The sample elements excited are chosen by taking as the lower limit the same ratio of
excitation line energy to element absorption edge as in Table 2 (approximately 0.45) and the·
requirement that the excitation line energy be above the element absorption edge as the upper
limit (L2 edges used for L lines). K-beta excitation lines were ignored.
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TABLE4
FIELD-BASED METHOD DETECTION LIMITS (mg/kg)'
Instrument
Analyte TN TN Lead X-MET920 X-MET 920 XL MAP
9000 Analyzer (Si Li (Gas-Filled Spectrum Spectrum
Detector) Detector) Analyzer Analyzer
Antimony 55 NR NR NR NR NR
Arsenic 60 50 55 50 110 225
Barium 60 NR 30 400 NR NR
Chromium 200 460 210 110 900 NR
Cobalt 330 NR NR NR NR NR
Coooer 85 115 75 100 125 525
Lead 45 40 45 100 75 165
Manqanese 240 340 NR NR NR NR
Molybdenum 25 NR NR NR 30 NR
Nickel 100 NR NA NA NA NR
Rubidium 30 NR NR NR 45 NR
Strontium 35 NR NR NR 40 NR
Tin 85 NR NR NR NR NR
Zinc 80 95 70 NA 110 NA
Zirconium 40 NR NR NR 25 NR
Source: Reference 4
a MDLs are related to the total number of counts taken. See Section 13.3 for count times
used to generate this table.
NR
NA
Not reported.
Not applicable; analyte was reported but was not at high enough concentrations for
method detection limit to be determined.
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Analyte
TN
9000
Antimony 6.54
Arsenic 5.33
Barium 4.02
Cadmium 29.84'
Calcium 2.16
Chromium 22.25
Cobalt 33.90
Copper 7.03
Iron 1.78
Lead 6.45
Manganese 27.04
Molybdenum 6.95
Nickel 30.85"
Potassium 3.90
Rubidium 13.06
Strontium 4.28
Tin 24.32'
Titanium 4.87
Zinc 7.27
Zirconium 3.58
. Source: Reference 4
TABLE 5
PRECISION
Average Relative Standard Deviation for Each Instrument
at 5 to 10 Times the MDL
TN Lead X-MET 920 X-MET 920 XL MAP
Analyzer (Si Li (Gas-Filled Spectrum Spectrum
Detector) Detector) Analyzer Analyzer
NR NR NR NR NR
4.11 3.23 1.91 12.47 6.68
NR 3.31 5.91 NR NR
NR 24.80' NR NR NR
NR NR NR NR NR
25.78 22.72 3.91 30.25 NR
NR NR NR NR 1-.JR
9.11 8.49 9.12 12.77 14.86
1.67 1.55 NR 2.30 NR
5.93 5.05 7.56 6.97 12.16
24.75 NR NR NR NR
NR NR NR 12.60 NR
. NR 24.92' 20.92" r-JA NR
NR NR NR NR NR
NR NR NR 32.69' NR
NR NR NR 8.86 NR
NR NR NR NR NR
NR NR NR NR NR
7.48 4.26 2.28 10.95 0.83
NR NR NR 6.49 NR
a These values are biased high because the concentration of these analytes in the soil
samples was near the detection limit for that particular FPXRF instrument.
Not reported. NR
NA Not applicable; analyte was reported but was below the method detection limit.
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TABLE 6
PRECISION AS AFFECTED BY SAMPLE PREPARATION
Average Relative Standard Deviation for Each Preparation Method
Analyte Intrusive-Intrusive-
In Situ-Field Undried and Unground Dried and Ground
Antimony 30.1 15.0 14.4
Arsenic 22.5 5.36 3.76
Barium 17.3 3.38 2.90
Cadmium' 41.2 30.8 28.3
Calcium 17.5 1.68 1.24
Chromium 17.6 28.5 21.9
Cobalt 28.4 31.1 28.4
Copper 26.4 10.2 7.90
Iron 10.3 1.67 1.57
Lead 25.1 8.55 6.03
Manganese 40.5 12.3 13.0
Mercury ND ND ND
Molybdenum 21.6 20.1 19.2
Nickel' 29.8 20.4 18.2 ' Potassium 18.6 3.04 2.57
Rubidium 29.8 16.2 18.9
Selenium ND 20.2 19.5
Silver' 31.9 31.0 29.2
Strontium 15.2 3.38 3.98
Thallium 39:0 16.0 19.5
Thorium NR NR NR
Tin ND 14.1 15.3
Titanium 13.3 4.15 3.74
Vanadium NR NR NR
Zinc 26.6 13.3 11.1
Zirconium 20.2 5.63 5.18
Source: Reference 4
' . These values may be biased high because .the concentration of these analytes in the soil
samples was near the detection limit.
ND
NR
Not detected.
Not reported.
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TN 9000
Analyte n Range Mean SD
of % Rec.
·% Rec.
Sb 2 100-149 124.3 NA
As 5 68-115 92.8 17.3
Ba 9 98-198 135.3 36.9
Cd 2 99-129 114.3 NA
Cr 2 99-178 138.4 NA
Cu 8 61-140 95.0 28.8
Fe 6 78-155 103.7 26.1
Pb 11 66-138 98.9 19.2
Mn 4 81-104 93.1 9.70
Ni ·3 99-122 109.8. 12.0
Sr 8 110-178 132.6 23.8
Zn 11 41-130 94.3 24.0
Source: Reference 4
n
--
5
--
--
--
6
6
11
3
--
--
10
TABLE 7
ACCURACY
Instrument
TN Lead Analyzer
Range Mean SD
of %
% Rec. Rec.
------
44-105 83.4 23.2
------
------
------
38-107 79.1 27.0
89-159 102.3 28.6
68-131 97.4 18.4
92-152 113.1 33.8
------
------
81-133 100.0 19.7
X-MET 920 (SiLi Detector) XL Spectrum Analyzer
n Range Mean SD n Range Mean SD
of % of %
% Rec %Rec. Rec.
Rec.
----------------
4 9.7-91 47.7 39.7 5 38-535 189.8 206
9 18-848 168.2 262 --------
6 81-202 110.5 45.7 --------
7 22-273 143.1 93.8 3 98-625 279.2 300
11 10-210 111.8 72.1 8 95-480 203.0 147
6 48-94 80.4 16.2 6 26-187 108.6 52.9
12 23-94 72.7 20.9 13 80-234 107.3 39.9
----------------
--------3 57-123 87.5 33.5
--------7 86-209 125.1 39.5
12 46-181 106.6 34.7 11 31-199 94.6 42.5
n Number of samples that contained a certified value for the analyte and produced a detectable concentration from the FPXRF instrument.
SD Standard deviation.
NA Not applicable; only two data points. therefore, a SD was not calculated.
%Rec. Percent recovery.
No data.
CD-ROM 6200 -23 Revision 0
January 1998
Standard · Arsenic
Reference
Material Cert. Meas. %Rec. Cert.
Cone. Cone. Cone.
RTC CRM-021 24.8 ND NA 586
RTC CRM-020 397 429 92.5 22.3
BCRCRM 143R --------
BCR CRM 141 -------
USGS GXR-2 25.0 ND NA 2240
USGSGXR-6 330 294 88.9 1300
NIST 2711 105 104 99.3 726
NIST 2710 626 722 115.4 707
NIST 2709 17.7 ND NA 968
NIST 2704 23.4 ND NA 414
CNRC PACS-1 211 143 67.7 --
SARM-51 - ---335
SARM-52 -----410
Source: Reference 4
%Rec.
ND
NA
All concentrations in milligrams per kilogram.
Percent recovery.
Not detected.
Not applicable.
No data.
CD-ROM
TABLE 8
ACCURACY FOR TN 9000'
Barium Copper
Meas. %Rec. Cert. Meas.
Cone. Cone. Cone.
1135 193.5 4792 2908
ND NA 753 583
----131 105
----32.6 ND
2946 131.5 76.0 106
2581 198.5 66.0 ND
801 110.3 114 ND
782 110.6 2950 2834
950 98.1 34.6 ND
443 107.0 98.6 105
772 NA 452 302
466 139.1 268 373
527 128.5 219 193
6200 -29
Lead
%Rec. Cert. Meas.
Cone. Cone.
60.7 144742 149947
77.4 5195 3444
80.5 180 206
NA 29.4 ND
140.2 690 742
NA 101 80.9
NA 1162 1172
96.1 5532 5420
NA 18.9 ND
106.2 161 167
66.9 404 332·
139.2 5200 7199
. 88.1 1200 1107
%Rec.
103.6
66.3
114.8
NA
107.6
80.1
100.9
98.0
NA
103.5
82.3
138.4
92.2
Zinc
Cert. Meas. %Rec.
Cone. Cone.
546 224 40.9
3022 3916 129.6
1055 1043 99.0
81.3 ND NA
530 596 112.4
118 ND NA
350 333 94.9
6952 6476 93.2
106 98.5 93.0
438 427 97.4
824 611 74.2
2200 2676 121.6
264 215 81.4
Revision 0
January 1998
TABLE 9
REGRESSION PARAMETERS FOR COMPARABILITY'
Arsenic Barium
n r2 Int. Slope n r' Int. Slope
~II Data 824 0.94 1.62 0.94 1255 0.71 60.3 0.54
ISoil 1 368 0.96 1.41 0.95 393 0.05 42.6 0.11
Soil2 453 0.94 1.51 0.96 462 0.56 30.2 0.66
IISoil 3 - - ---400 0.85 44.7 0.59
Prep 1 207 0.87 2.69 0.85 312 0.64 53.7 0.55
Prep 2 208 0.97 1.38 0.95 315 0.67 64.6 0.52
Prep 3 204 0.96 1.20 0.99 315 0.78 64.6 0.53
Prep 4 205 0.96 1.45 0.98 313 0.81 58.9 0.55
Lead Zinc
n r2 Int. Slope n ,. Int. Slope '
i"-11 Data 1205 0.92 1.66 0.95 1103 0.89 1.86 0.95
Soil 1 357 0.94 1.41 0.96 329 0.93 1.78 0.93
ISoil 2 451 0.93 · 1.62 0.97 423 0.85 2.57 0.90
Soil 3 397 0.90 2.40 0.90 351 0.90 1.70 0.98
Prep 1 305 0.80 2.88 0.86 286 0.79 3.16 0.87
Prep 2 298 0.97 1.41 0.96 272 0.95 1.86 0.93
Prep 3 302 0.98 1.26 0.99 274 0 93 _ 1.32 1.00
Prep4 300 0,96 1.38 1.00 271 0.94 1.41 1.01
Source: Reference 4
Log-transformed data
n Number of data points
r2 Coefficient of determination
Int. Y-intercept
No applicable data
CD-ROM 6200 -30
n
984
385
463
136
256
246
236
246
n
280
-
-
186
105
77
49
49
Copper
r2 Int. Slope
0.93 2.19 0.93
0.94 1.26 0.99
0.92 2.09 0.95
0.46 16.60 0.57
0.87 3.89 0.87
0.96 2.04 0.93
0.97 1.45 0.99
0.96 1.99 0.96
Chromium
r'
0.70
-
-
0.66
0.80
0.51
0.73
0.75
Int. Slope
64.6 0.42
- -
- -
38.9 0.50
66.1 0.43
81.3 0.36
53.7 0.45
31.6 0.56
Revision 0
January 1998
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APPENDIX B
QUALITY ASSURANCE/QUALITY CONTROL MANUAL
ANALYTICAL SERVICES, INC.
{ELECTRONIC SUBMITTAL)
15