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Oak Ridge Reservation
Environmental Health Archives
Current as of 10FEB99
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Captain John R. Stockwell, M.D., M.P.H.
U.S. Public Health Service
Florida State University's Scarboro Sample
Analysis Protocol
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Florida State
UNIVERSITY
Department of Oceanography
Environmental Radioactivity Measurement Facility
Tallahassee, Florida 32306-4320 U.S.A.
850-644-6703 • FAX 850-644-2581
E-mail burnett@ocean.fsu.edu
April 15, 1998
MEMORANDUM
TO: Environmental Management Technical Services Team
DOE Oak Ridge Operations
Prof. Larry Robinson
Florida A&M University
FROM: William C. Burnett
Florida State University
RE: Technical Memorandum Regarding Scarboro Sample Analysis
Introduction
The purpose of this memorandum and accompanying information is to clearly define the
analytical methods and the quality assurance procedures to be followed by Florida State
University (FSU) during the analysis of the environmental samples from the Scarboro
Community.
Analytical Methods
FSU will analyze the Scarboro Community samples using the techniques and stated MDA's
given in Table 1 of the Jacobs EM Report dated MarcH30; 1998 With one exception.': We have
elected to perform the iSotopic uranium in water via alpha-spectrometry.rather than gamma
spectrometry as mentioned in the report. We feel this will offer more precise results with 234U
isotopic information as well as<238U and 235U.
US EPA REGION 4 LIBRARY
AFC-TOWER 9™ FLOOR
61 FORSYTH STREET SW
ATLANTA, GA. 30303
All other analyses will be performed in line with the specifications of Table 1. Specific details
are provided in the written procedures includedwith- the binder delivered with this1 memorandum.
-------
digestion in nitric acid using an Environmental Express Hot Block, a wet oxidation procedure to
reduce color to the extent possible, and counting via a liquid scintillation counter with alpha/beta
discrimination. Quench curves for both alpha (241Am) and beta (90Sr) will be run over the region
represented by the samples. Water samples will be preconcentrated by evaporation and then run
by the same procedure as the soil samples. Uranium, thorium, and plutonium isotopes in water
will be preconcentrated by a calcium phosphate co-precipitation followed by chemical separation
using extraction chromatographic techniques. Sources for alpha spectrometry will be prepared
by cerium fluoride microprecipitation and filtration. These same isotopes will also be determined
by alpha spectrometry for soil samples after a Hot Block nitric acid digestion. Radioactive
tracers (232U, 228Th, and 242Pu) will be added to all samples, as early in the procedure as possible,
for assessment of chemical recoveries. Strontium-90 in soils and water will be performed
following procedure RP500 from the DOE Compendium of Methods (1997). We will use
Eichrom's Sr Resin for separation and purification of Sr and use liquid scintillation counting for
measurement. Isotopic uranium and a full gamma scan to 2000 keV will be performed using a
method based on EML's HASL-300 Procedures Manual with a modification for measurement of
absorption of low-energy gamma-emitters. A table of the nuclides that will be addressed together
with energies and estimated MDA's is given in the gamma spectrometry protocol. In addition,
we have also provided a complete description of the transmission-based absorption correct used
in our laboratory. Gamma spectrometry will also be used to quantify Cs-137 in soil/sediment
and water.
Quality Control Practices
The Environmental Radioactivity Measurement Facility at FSU has been active in several blind
intercomparison programs over the past decade. These programs are run by national and
international organizations including the Environmental Protection Agency (EPA), DOE's
Environmental Measurements Laboratory (EML), and the International Atomic Energy Agency
(IAEA). Results for the past two years from these "performance-based" evaluations have
already been supplied to the Environmental Management Technical Services Team during their
recent laboratory audit. We have performed well in these programs and plan to continue to
participate to the extent possible.
Our laboratory also maintains routine QC checks of all counting instruments to ensure that they
are operating within expected specifications. Each instrument has a written procedure for the QC
check which details the protocol, time intervals, reporting, etc. We have included copies of the
QC protocols for all the instruments which will be used for the Scarboro Project, i.e., alpha
spectrometers, liquid scintillation counter, and intrinsic germanium detector.
In addition to our normal QC practices, we plan to include the following action items for the
Scarboro Sample Analysis: (1) A project-specific notebook will be maintained with all relevant
-------
information as outlined in Appendix A from the laboratory audit report; (2) Calibrated weights
will be purchased and a daily analytical balance check performed; (3) Daily efficiency and energy
calibration of the gamma spectrometer will be conducted; and (4) Separate file folders will be kept
for all raw data together with copies of QC and background data for submission together with the
final report.
Sample Custody
FSU will cooperate closely with FAMU concerning custody of samples. All samples will be
delivered to FAMU where they will be kept in a locked room. Analysts from FSU will work
with FAMU personnel on as much as the sample preparation as possible in the FAMU facility.
For example, the soils can be dried and homogenized before aliquots are taken for analysis at
FSU. We will then take only the aliquot size required for each of our analyses which will allow
us much better control over these samples. We will maintain a cabinet in room 302 of the FSU
Oceanography/Statistics Building which will be pad-locked and used exclusively for the Scarboro
Project. All samples will be kept in that cabinet except for those actually in process. Any
remaining sample materials will be returned to FAMU after the analyses are complete.
Personnel
Dr. William C. Burnett will supervise all aspects of this work. Dr. Burnett has over 25 years
experience in the measurement of radioactive species in environmental samples. The principal
bench chemist for this project will be Mr. Alan Baker who has over 4 years experience working
in our laboratory. He is particularly well-suited for the analyses involving gamma spectrometry
and alpha spectrometry because of his past experience in these areas. We also plan to have Mr.
Peter Cable assist us during the early stages of the project. Mr. Cable worked in our laboratory
for 8 years and is familiar with all the analyses being performed for this project. He also has
experience working with two commercial laboratories (QST Environmental and Environmental
Physics, Inc.) and is now working part time in a radiochemistry laboratory at Tulane University.
Peter is available to work with us in our laboratory for approximately 2-3 weeks after receipt of
samples. We plan to have him get the bulk of the radiochemical separations (U, Th, Pu, Sr-90)
accomplished during this time. Roger Wong, a graduate student just finishing his M.S. in
environmental radiochemistry, may also assist us on certain parts of the project.
Curriculum vitae of all FSU personnel are included with the binder,
encl. FSU Analytical Methods and Quality Control Practices (Binder)
-------
PREPARATION OF WATER SAMPLES FOR ANALYSIS BY ALPHA
SPECTROMETRY
1.0 PURPOSE
This procedure provides instructions for preparation of natural water
samples for the analysis of actinide elements by alpha spectrometry. The
protocol entitled "Radiochemical Separations For Analysis of U, Th, Am,
And Pu Isotopes By Alpha Spectrometry" should be followed after
completion of the procedures detailed here. Water samples for gross
alpha/beta will simply be evaporated to dryness before proceeding with the
same method as used in the soil protocol.
2.0 SCOPE
Water samples will be scavenged with CaHP04 to preconcentrate actinide
elements before chemical separation and analysis via alpha spectrometry.
Radioactive tracers are added early in the procedure to monitor recoveries of
the elements of interest. Calcium is added to the sample as a carrier and
phosphate is added either in the form of phosphoric acid or as the soluble
phosphatic salt, ammonium hydrogen phosphate.
3.0 RESPONSIBILITIES
Laboratory Chemists/Technicians/Analysts are responsible for following this
procedure, FSU safety rules, and other written instructions from technical
personnel and the laboratory manager. They must assess if an operation is
safe to continue and know how to follow the proper channels to stop work,
when appropriate. Laboratory personnel are to follow the QA/QC protocol
for all analytical operations and sample preparations. Vital sample
preparation and analytical data as directed by supervision must be recorded in
bound notebooks. Instrumentation used in the analysis and sample
preparation must be calibrated, and the calibration documented according to
established frequency. WTastes generated from this procedure must be
characterized and disposed of properly from a regulatory and environmental
perspective.
4.0 PROCEDURE
Reagents
Calcium nitrate (1.25M)-Dissolve 73 grams of Ca(NC>3)2-4H20 in 100 mL of
water and dilute to 250 mL with water (-50 mg Ca/mL).
-------
Ammonium hydrogen phosphate (3.2M)-Dissolve 106 grams of (NH.4)2HP04
in 200 mL of water, heat gently to dissolve, and dilute to 250 mL with water.
Or, Concentrated H3PO4
Concentrated NH4OH
Procedure
1. If not already prefiltered, filter the sample through a 0.45 micron filter or
allow particulates to settle and then carefully decant.
2. Aliquot 500 to 1000 mL of the filtered or decanted sample (or enough to
meet required detection limit) into an appropriate size beaker.
Appropriate amounts of the U-232, Th-228, Pu-242, and Am-243 are added
to each sample as required.
3. If samples have not been previously acidified, add 5 mL of concentrated
HC1 (sp gr 1.19) per liter of sample (0.5 mL per 100 mL) to acidify each
sample.
4. Put samples on a hotplate and bring to a boil for a few minutes to degas
C02.
5. Add 1 mL of 1.25M Ca(N03)2 to each beaker.
6. Add 3 mL of 3.2M (NH4)2HPC>4 or -1.5 mL conc. H3PO..
7. Add enough concentrated NH4OH to reach a pH>8 (check with pH strips)
and form Ca3(PC>4)2 precipitates. Stir with a glass of Teflon stirring rod for
a few minutes.
8. Either centrifuge the entire sample, or if the sample volume is too large,
allow precipitate to settle until solution can be decanted or aspirated (30
minutes to 2 hours) and then proceed with step 9.
9. Decant supernatant and discard to waste.
10. Transfer the precipitate to a centrifuge tube and centrifuge the precipitate
for approximately 10 minutes at 2000 rpm.
11. Decant supernatant and discard to waste.
12. Wash the precipitate (precipitate normally amounts to -3-4 mL) twice
with 5 mL of water, centrifuge and decant (and discard) the washes and go
to separation procedure for alpha spectrometry.
2 -) n !-f , 1 '
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PREPARATION OF SOILS AND SEDIMENT FOR ANALYSIS BY ALPHA
SPECTROMETRY AND GROSS ALPHA/BETA VIA LIQUID SCINTILLATION
COUNTING
1.0 PURPOSE
This procedure provides instructions for preparation of soils and sediment
via an acid digestion technique using the Environmental Express "Hot
Block." Water samples will be scavenged with CaHP04 to preconcentrate
actinides before chemical separation and analysis via alpha spectrometry. A
separate protocol is provided for this purpose. Water samples for gross
alpha/beta will simply be evaporated to dryness before proceeding with the
same method as used by soils.
2.0 SCOPE
This method is used to measure the nitric acid-leachable portion of soil and
sediment samples for uranium, thorium, and plutonium isotopes as well as
gross alpha and beta radioactivities. Filtered water samples are either
evaporated to dryness or scavenged by co-precipitation before proceeding with
the technique. The method is based on the assumption that
anthropogenically-derived radionuclides will be mobilized in strong mineral
acids using the technique described. Experiments in our laboratory (Smith,
1998) have shown that >97% of the 239-M0pu in a NIST natural-matrix
sediment SRM is removed by this treatment. NIST-traceable 2j2U, 228Th,
243Am, and 242Pu yield monitors are added during the treatment for alpha
spectrometry. No tracers are added for the gross alpha/beta procedure as
those activities are evaluated by independent calibration (see protocols for
calibration of the gross alpha/beta technique).
3.0 RESPONSIBILITIES
Laboratory Chemists/Technicians/Analysts are responsible for following this
procedure, FSU safety rules, and other written instructions from technical
personnel and the laboratory manager. They must assess if an operation is
safe to continue and know how to follow the proper channels to stop work,
when appropriate. Laboratory personnel are to follow the QA/QC protocol
for all analytical operations and sample preparations. Vital sample
preparation and analytical data as directed by supervision must be recorded in
bound notebooks. Instrumentation used in the analysis and sample
preparation must be calibrated, and the calibration documented according to
established frequency. Wastes generated from this procedure must be
characterized and disposed of properly from a regulatory and environmental
perspective.
-------
4.0 PROCEDURE
Digestion of Soils for Analysis by Alpha Spectrometry
1. Label a set of plastic Hot Block tubes with the appropriate sample numbers
using a permanent marker.
2. Weigh out approximately 1 gram of dried and homogenized soil to an
uncertainty of ±0.2 mg using an analytical balance. Put each soil sample
into the appropriate plastic tube.
3. Add the appropriate amounts of 232U, 228Th, and 242Pu tracers using a
calibrated pipette.
if
4. Add mL of^M HN03 to each tube.
5. Place all tubes, with loose-fitting watch-glass covers, into the Hot Block.
Adjust the temperature setting to 90°C.
6. Allow the samples to reflux with the HN03 for 4 hours. Add additional
HN05 if necessary to ensure that the volumes do not fall below 10 mL.
Using the gradations on the plastic tubes, adjust the volume back to38 mL
with/£M HN03 if necessary at the end of the experiment. /?"
£l{
7. Remove all the tubes from the unit and allow them to cool. Balance in
pairs using the counter-weight scale in preparation for centrifugation.
Replace the tops with the tight-fitting plastic caps.
8. Centrifuge at 2500 rpm for 5 minutes or until a clear separation between
sample and fluid is ensured.
9. Decant the HN05 from each sample into a new set of clean, pre-labeled
plastic tubes.
10. AddJUTmL double deionized water (DDW) to each soil sample and stir to
suspend the sample. Centrifuge, decant into the same plastic tubes.
Repeat using 5 ijiL of DDW. The sample should now consist of
approximately^TmL of 2-2.5M HN03 which will be the load solution for
the column separations (see separate protocol).
-------
Digestion of Soils for Gross a/ft Radioactivities via Liquid Scintillation Counting
1. Label a set of plastic Hot Block tubes with the appropriate sample numbers
using a permanent marker.
2. Weigh out approximately 1 gram of dried and homogenized soil to an
uncertainty of ±0.2 mg using an analytical balance. Put each soil sample
into the appropriate plastic tube.
3. Add 20 mL of 4M HN03 to each tube.
4. Place all tubes, with loose-fitting watch-glass covers, into the Hot Block.
Adjust the temperature setting to 90°C.
5. Allow the samples to reflux with the HN03 for 4 hours. Add. additional
HN03 if necessary to ensure that the volumes do not fall below 10 mL.
7. Remove all the tubes from the unit and allow them to cool. Balance in
pairs using the counter-weight scale in preparation for centrifugation.
Replace the tops with the tight-fitting plastic caps.
8. Centrifuge at 2500 rpm for 5 minutes or until a clear separation between
sample and fluid is ensured.
9. Decant the HN03 from each sample into prelabeled 20-mL glass
scintillation vials. Evaporate to dryness.
10. Add 10 mL double deionized water (DDW) to each sample and stir to
suspend the sample. Centrifuge, decant into the same prelabeled 20-mL
glass scintillation vials. Repeat using 5 mL of DDW. Evaporate to dryness.
11. Add a few mL HN03 and a few drops H202. Bring to dryness without
baking. Treat residue repeatedly with HN03/H202 until there is no further
color change. The objective here is to lighten the color to the extent
possible to decrease quenching.
12. Add 2 mL 1M HN03 to glass scintillation vial to pick up residue. Transfer
to plastic 20-mL liquid scintillation vial. Add another 2 mL 1M HNOa to
complete the transfer. Add 16 mL of Ultima Gold A/B cocktail and seal
the vial with plastic cap. The sample is now ready for LSC via the
appropriate protocol.
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RADIOCHEMICAL SEPARATIONS FOR ANALYSIS OF U, TH, AM, AND PU
ISOTOPES BY ALPHA SPECTROMETRY
1.0 PURPOSE
This procedure provides instructions for radiochemical separation of
soil/sediment samples that have already been prepared via the Hot Block acid
digestion technique. NIST-traceable 232U, 228Th, 243Am, and 242Pu yield
monitors have already been added during the preliminary treatments. Water
samples may be either scavenged with Fe(OH)3/ CaHP04, or simply
evaporated to dryness before proceeding with the same method.
2.0 SCOPE
This method is used to measure the nitric acid-leachable portion of the soil
and sediment samples for alpha and beta radioactivity and the soluble portion
of filtered water samples. This procedure provides instructions for separation
of U, Th, Am, and Pu from each other as well as common constituents in
environmental samples. The preparation of the final sources via CeF3
microprecipitation and filtration is also provided.
The method is divided into a "2-column" and a "3-column" procedure. The
2-column procedure is intended for water samples and other lightly-loaded
samples (e.g., soil samples of 1 gram or less). The 3-column procedure is
preferred for more heavily-loaded samples and when Th/Np separations are
important.
3.0 TERMS/DEFINITIONS
1. Extraction chromatographic resins - these are specialized resins that are
made by impregnation of organic extractants onto inert plastic beads. The
resins have been shown to be highly selective for certain elements or
certain groups of elements (e.g., "TEVA-Resin" will extract the tetravalent
actinide group of elements). The resins are available commercially from
Eichrom Industries, Inc.
2. Elution - the process of removal of an element from a column by addition
of an acid or reagent which will cause it to be released. This is often
accomplished by addition of something that changes the chemical state
(and thus behavior) of an ion or has a significant effect on the distribution
coefficient for that ion.
-------
3. Source - the form of the sample that may be introduced to the alpha
spectrometer. Ideally, the source should be thin, uniform, and contain
isotopes of only one element.
4.0 RESPONSIBILITIES
Laboratory Chemists/Technicians/Analysts are responsible for following this
procedure, FSU safety rules, and other written instructions from technical
personnel and the laboratory manager. They must assess if an operation is
safe to continue and know how to follow the proper channels to stop work,
when appropriate. Laboratory personnel are to follow the QA/QC protocol
for all analytical operations and sample preparations. Vital sample
preparation and analytical data as directed by supervision must be recorded in
bound notebooks. Instrumentation used in the analysis and sample
preparation must be calibrated, and the calibration documented according to
established frequency. Wastes generated from this procedure must be
characterized and disposed of properly from a regulatory and environmental
perspective.
5.0 PROCEDURE
Reagents
Aluminum nitrate, A1(N03)3 - 1.0M
Ammonium bioxalate, (NH4)2C204#H20 - 0.1M
Ammonium hydroxide, NH.OH - concentrated
Ascorbic acid
Cerium carrier - 0.5 mg Ce/mL
Double deionized water, DDW
Ethanol - 80%
Ferrous sulfamate solution - Strem Chemical Co. 40%-50% aqueous, or -1.8M
Hydrazine dihydrochloride - 25% solution
Hydrochloric acid, HC1 - concentrated, 9M, 6M, 4M, and 0.01M
Hydrochloric-oxalic acid - 5M HC1 / 0.05M oxalic
Hydrofluoric acid, HF - concentrated
Hydrogen peroxide, H;02 - 30%
Nitric acid, HNOs - concentrated, 5M, 2.5M
Nitric acid sodium nitrite solution - 2.5M HN03 / 0.1M NaN02
Titanium trichloride, TiCl3 - 10% wt solution in 20%-30% HC1 (Aldrich Chemical
Co.)
TEVA* Resin - 100-150 ^.m particle size
TRU# Resin - 100-150 jim particle size
UTEVA*Resin - 100-150 particle size
-------
Two Column Separation - UTEVA/TRU Resin
1. Add sufficient A1(N03)3 reagent to the 2.5M HN03 solution from the sample
preparation protocol to make the load solution 2.5M HN03 / 0.5M A1(N03)3.
Swirl to mix.
2. For each sample solution, place one UTEVA* Resin and one TRU* Resin
column in the column rack in a tandem fashion (i.e., the washings from the
UTEVA «Resin column will drain into the reservoir of the TRU •Resin
column).
3. Place a waste beaker below each pair of columns. Pipette 5 mL of 2.5M HN03
into the UTEVA*Resin column of each column pair to condition the resin
and allow to drain.
4. Add 1 mL Strem ferrous sulfamate solution for each 10 mL of load solution to
the centrifuge tube from step 2. Swirl to mix.
5. Add -100 mg ascorbic acid to each centrifuge tube, swirling to mix. Allow the
ascorbic acid to completely dissolve (about 5 minutes). The solution should
be a light green color.
6. Transfer this load solution to the top reservoir of a column pair by pouring or
transfer pipette. Discard eluent.
7. Rinse the centrifuge tube with 5 mL of 2.5M HN03 and 0.2 mL Strem ferrous
sulfamate solution, and add to the top reservoir of the column pair. Discard
eluent.
8. Repeat step 8.
9. Disconnect the column pair and run the UTEVA*Resin and TRU*Resin
columns separately, and simultaneously.
(All solutions are added directly to the columns)
UTEVA*Resin Column:
1. Pipette 15 mL of 2.5M HNO, to rinse out the ferrous sulfamate. Discard.
2. Pipette 2 mL of 9M HC1 to convert to the chloride system. Discard.
3. Thorium elution. Place a clean plastic beaker labeled with the sample number
and "Th" under the column. Pipette 20 mL of 5M HC1 / 0.05M oxalic acid.
Set aside for source preparation.
4. Uranium elution. Place a clean plastic beaker labeled with the sample number
and "U" under the column. Pipette 15 mL of 0.01M HC1. Collect and save
this elution. Set aside for source preparation.
TRU*Resin Column:
1. Pipette 5 mL 2.5M HNO- to rinse ferrous sulfamate. Discard.
2. Pipette 5 mL 2.5M HN03 / 0.1M NaNO-,. Allow to drain completely. Discard.
3. Pipette 5 mL 2.5M HN03 to rinse out NaNOz. Discard.
4. Americium elution. Place a clean plastic beaker labeled with the sample
number and Am" under the column. Pipette 2 mL of 9M HC1 to convert to
the chloride system. Allow to drain. Pipette 20 mL of 4M HC1. Set aside for
source preparation.
-------
5. Plutonium elution. Place a clean plastic beaker labeled with the sample
number and "Pu" under the column. Pipette 20 mL of 0.1M ammonium
bioxalate. Collect and save this elution. Set aside for source preparation.
Three Column Separation - TEVA/UTEVA/TRU Resin
1. Add sufficient A1(N03)3 reagent to the 2*5M HN03 solution from the sample
preparation protocol to make the load solution 2.5M HNOa / 0.5M A1(N03)3.
Swirl to mix.
2. For each sample solution, place one TEVA* Resin, one UTEVA* Resin, and one
TRU* Resin column in the column rack in such a manner that the
washings from the TEVA* Resin column drain into the reservoir of the
UTEVA*Resin column, which in turn will drain into the reservoir of the
TRU • Resin column.
3. Place a waste beaker below each set of columns. Pipette 5 mL of 2.5M HN03
into the UTEVA*Resin column of each column set to condition the resin
and allow to drain.
4. Add 1 mL Strem ferrous sulfamate solution for each 10 mL of load solution to
the centrifuge tube from step 2. Swirl to mix.
5. Add -100 mg ascorbic acid to each centrifuge tube, swirling to mix. Allow the
ascorbic acid to completely dissolve (about 5 minutes). The solution should
be a light green color.
6. Transfer this load solution to the top reservoir of each column set by pouring
or uses of a transfer pipette. Discard eluent.
7. Rinse the centrifuge tube with 5 mL of 2.5M HN03 and 0.2 mL Strem ferrous
sulfamate solution, and add to the top reservoir of the column pair. Discard
eluent.
8. Repeat step 8.
9. Disconnect the TRU*Resin column, leaving the TEVA*Resin column and the
UTEVA *Resin column in tandem.
TEVA*Resin - UTEVA*Resin tandem:
1. Pipette 20 mL of 2.5M HN03 to rinse out the uranium.
2. Disconnect the column pair.
3. Thorium elution. Place a cl^n plastic beaker labeled with the sample number
and "Th" under th^ccHumn5? Hpette 15 mL of 6M HC1. Collect and save
this elution. Set aside for source preparation.
From this point on, the TRU*Resin column and the UTEVA*Resin column may be
run exactly as described in the two-column separation procedure, except for the
UTEVA*Resin column, skip step 1.
-------
Source Preparation
1. The Th, Am, and Pu final solutions should first be evaporated in the presence
of HN03 and H202 to oxidize any organic extractant that may come off the
columns. Repeat as necessary until no visible residue remains. Pick up in
10 mL of 2M HC1.
2. Add 50 /ig (100 mL of carrier solution) of cerium to the plastic beakers
containing the final elutions for uranium and plutonium.
3. Add 0.5 mL of TiCl3 to the uranium elution, and 2-3 drops of 25% hydrazine
dihydrochloride solution to the plutonium elution. Allow to stand for
several minutes.
4. Add 1-2 mL concentrated HF to each beaker. Swirl to mix. Let the solutions sit
for at least 20 minutes before filtering.
5. Set up a 0.1 micron 25-mm membrane filter, glossy side down, on a filter
apparatus.
6. Add 3-5 mL 80% ethanol to wet the filter. Apply vacuum. Add 2-3 mL DDW.
7. Filter the sample. Rinse the plastic beaker with ~5 mL DDW and filter. Make
sure to rinse down the inside of the filter funnel.
8. Wash the filter with 3-5 mL 80% ethanol. Again, make sure to rinse down the
inside of the filter funnel.
9. Remove the filter and place in a plastic filter holder. Dry in a low temperature
(60°C) oven for a few minutes.
10. Mount filter on a 1.25-inch stainless steel planchet. Count by alpha
spectrometry.
-------
Laboratori'/Radiochemislry
RP500(a)
Purification of Strontium in Water Before Strontium-89/Strontium-90
Measurement
1.0 Scope and Application
This method forms the basis for analyzing radioactive Sr (isotopes 89 and/or 90) in surface and
groundwaters (including, but not limited to, drinking water). It applies to any sample volume
that can be preconcentrated and redissolved in less than 20 mL of column feed solution. The
detection limit depends on sample volume and counting protocol. After preconcentration, the
chemistry takes about 4 h and is amenable to being batched (i.e., one person can process many
samples simultaneously). Chemical waste per sample is approximately 30 mL S M HNO^ plus
a spent column, a dramatic reduction compared to traditional radiostrontium analytical
methods.
2.0 Summary of Method
A yield monitor (normally stable Sr or 85Sr) is added to the sample. Large samples are reduced
in volume by evaporation, by cation exchange, or by coprecipitation (e.g., calcium carbonate or
calcium phosphate). The sample is re-dissolved in column feed solution and passed through a
Sx*Spec® column where Sr is selectively extracted into the column packing (crown ether
supported on an inert substrate). Virtually all other elements (with the notable exceptions of
Pb, Pu, and Np) are washed through the column. Strontium is then eluted with 0.05 M HNO,,
leaving Pb on the column. A Sr counting source is produced and counted using any of several
options.
3.0 Interferences and Limitations
3.1 Stable Sr present in the sample will interfere with the gravimetric yield determination.
If the Sr content in the sample is unknown, it should be determined {e.g., by atomic
absorption (AA), inductively coupled plasma (ICP). or by a duplicate sample run with
no added Sr carrier} so that appropriate adjustment can be made to the amount of Sr
recovered.
3.2 Stable Sr will consume column capacity. The maximum Sr that can be accommodated
by the Sr'Spec® column is approximately 10 mg Sr or 24 mg Sr(N03)->. An
appropriate working level is half that amount. Samples containing more than a few mg
of Sr may need to use smaller sample volumes or larger columns to avoid lowered Sr
recoveries.
(a) This method was supplied by D. M. Nelson (Argonne National Laboratory, Arconne, Illinois).
7 997
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DOF Methods
3.3 Lead and 210Pb are potentially serious interferences. Since Pb is more strongly bound to
the crown ether than is Sr, it will consume column capacity and displace Sr. More than a
few mg of Pb present in a sample will begin to decrease Sr recovery. Lead-210 itself is
well separated (by virtue of remaining on the column while Sr is eluted) and is not a
direct interference. Ingrowth of its daughter 210Bi during elution of Sr can be a problem
in samples that are high in 210Pb and low in radioactive Sr if a correction is not made for
the 210Bi.
3.4 Small amounts of the crown-ether extractant in the Sr eluent (due to column bleed) have
been observed and could cause interferences in the gravimetric yield calculation for direct
evaporation. The weight is reproducible (0.3 ± - 0.1 mg per 10 mL of column eluate),
and the presence of the crown ether acts as a binder for the S^NO^),. It causes no
problem so long as its mass is subtracted from the Sr(N03)2 mass.
3.5 The Pu(IV) and Np(IV) are retained on the Sr*Spec® column under high-acid conditions
and are eluted with Sr. This may cause interferences in subsequent beta counting if no
alpha/beta discrimination is employed. This interference can be removed by passing the
sample solution through an anion exchange column (to remove the Pu and/or Np) before
the solution is applied to the Sr'Spec® column.
3.6 This procedure has not been tested with all possible matrices and interferences. Before
use, it should be thoroughly tested for suitability on the specific waters of interest.
4.0 . Safety
No significant safety problems are presented by this method other than the normal precautions for
handling radioactive materials, acids, and bases.
5.0 Apparatus and Materials
Beta detector - proportional counter, liquid scintillation counter, or Cerenkov counter
• Sr»Spec® column - 2 mL (0.7 g) of resin, available prepacked from Eichrom Industries,
Inc., 8205 S. Cass Ave., Suite 107, Darien, IL, 60561 (800) 422-6693
• Counting containers - scintillation vials for liquid scintillation or Cerenkov counting, or
stainless steel dishes for proportional counting (A dish with tapered sides is essential for
maintaining a reproducible counting geometry.)
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Laboratorv/Radiochemistry
6.0 Reagents (purification procedure only)
• Nitric acid, 8 M
Nitric acid, 0.05 M
Column feed solution - 0.5 M A1(N03)3 in 8 M HN03 (Pure 8 M HN03 is an acceptable
alternative; Al(N03)3 enhances the affinity for Sr and improves the separation from Ba.)
• Strontium carrier - 10.0 mg/mL Sr(N03)2 in 0.1 M HN03
7.0 Sample Collection, Preservation, and Handling
Samples may be acidified to pH 1 with HN03 before sub-sampling.
8.0 Procedure
This procedure consists of
• several optional pre-concentration methods (A choice can be made based on sample
characteristics, or another appropriate pre-concentration method can be used.)
a method to isolate and purify the Sr fraction
several detection methods (A choice can be made based on data quality needs, or another
appropriate counting method can be used.)
Two options for determining chemical recover}' are suggested, by measuring stable Sr {either
by weighing the Sr(N03)2 residue or by instrumental analyses of Sr, e.g., by AA or ICP) or by
gamma counting of 85Sr (added as a tracer). Either may be chosen, but using stable Sr introduces
no counting interferences and is generally more appropriate for proportional or liquid scintillation
counting. Strontium-85, on the other hand, is suitable for Cerenkov counting or when is to
be extracted and counted by any method. These pre-concentration and counting options are not
meant to be exclusive, but are presented as illustrations of how this Sr purification scheme can be
applied. Samples expected to have sufficient radioactive Sr to meet data quality objectives
without pre-concentration may simply be acidified with HN03, have the appropriate yield
monitor added, and be loaded directly on the Sr*Spec® column.
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DOE Methods
8.1 Preconccntralion Method 1 - Evaporation
This method is used to transpose the sample to the column feed solution where only
acid soluble residues are formed by evaporation. Recovery is essentially quantitative.
8.1.1 An appropriately sized aliquot should be measured and transferred to a glass
beaker.
8.1.2 A known amount of Sr carrier (e.g., 1.00 mL) and/or of ^5Sr is added.
8.1.3 The solution is evaporated to dryness on a hotplate using moderate heat.
8.1.4 The sides of the beaker are washed with a few mL of 8 M HN03.
8.1.5 The solution is evaporated to incipient dryness and redissolved in a minimum
volume of feed solution (5 to 10 mL); the beaker is covered with a watchglass
and heated gently if necessary to dissolve the residue.
5.2 Preconcentration Method 2 - Cation Exchange
This method is used to transpose the sample to column feed solution where insoluble
residues (for example, CaS04) are formed during evaporation. Recover)' is essentially
quantitative.
8.2.1 An appropriately sized aliquot should be measured and transferred to a bottle.
8.2.2 A known amount of Sr carrier (e.g., 1.00 mL) and/or of 85Sr is added.
8.2.3 A cation exchange column containing 10 mL of AG 50W-X8 cation exchange
resin (100 to 200 mesh) is prepared. This column size is adequate for 1 L of
most fresh waters. Samples having high dissolved solids may need a larger
column. A simple visual test of the adequacy of the column size is
accomplished by adding 10 mc of copper {as Cu(N03), in 0.1 M HN03) to the
column just before the sample is passed. Retention of the blue Cu band on the
column is assurance that Sr (which is bound more strongly than is Cu) has been
retained.
8.2.4 The column is preconditioned with 50 mL of 0.1 M HN03.
8.2.5 The sample is passed through the column at a rate of -1 to 2 mL/min.
8.2.6 The column is rinsed with 50 mL of 0.1 M HNCL.
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Laboratory/Radiochemistry
8.2.7 The feed and rinse solutions are discarded.
8.2.8 . The Sr and other cations are eluted with 50 mL of 8 M HN03 into a beaker.
8.2.9 The solution is evaporated to dryness on a hotplate (the sample redissolves easily
if the evaporation is stopped just as the sample starts to go dry).
8.2.10 The salts are dissolved in a minimum volume of feed solution (5 to 10 mL),
covered with a watchglass, and heated gently if necessary to dissolve the
residues.
8.3 Preconcentration Method 3 - Calcium Phosphate Precipitation
This method or some variation can be used for most waters. Recovery is not quantitative,
but should exceed 709c.
8.3.1 An appropriately sized aliquot should be measured and transferred to a beaker.
8.2.2 A known amount (e.g., 1.00 mL) of Sr carrier and/or of 85Sr is added.
8.3.3 Calcium carrier is added while stirring (100 mg Ca/L of sample).
8.3.4 Phosphate is added while stirring (2 g phosphate/L of water, as phosphoric acid
or ammonium phosphate).
8.3.5 The solution is neutralized with an excess of ammonium hydroxide while
stirring.
8.3.6 The precipitate is collected by settling and/or centrifugation.
8.3.7 The precipitate is dissolved in a few mL of 8 M HN03. transferred to a small
beaker, evaporated to near dryness, and dissolved in a minimum volume of feed
solution (5 to 10 mL).
5.4 Preconcentration Method 4 - Calcium Carbonate Precipitation
This method or some variation can be used for most waters. Recovery is not quantitative,
but should exceed 70%.
8.4.1 An appropriately sized aliquot should be measured and transferred to a beaker.
8.4.2 A known amount (e.g., 1.00 mL) of Sr carrier and/or of ^5Sr is added.
1957
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PPiLMetftptff.
8.4.3 Calcium carrier is added while stirring (100 mg Ca/L of sample).
8.4.4 The solution is neutralized to pH 10 with 6 M NaOH while stirring.
8.4.5 Calcium carbonate is formed by adding 200 mL of 1.5 M Na^CO- per 1 L of
sample while stirring.
8.4.6 The precipitate is collected by settling and/or centrifugation.
8.4.7 The precipitate is dissolved in a few mL of 8 M HNO-j, transferred to a small
beaker, evaporated to near dryness, and dissolved in a minimum volume of feed
solution (5 to 10 mL).
8.5 Strontium Purification Procedure
This procedure uses the solution from one of the pre-concentration options as a starting
material and produces a solution from which a counting source is made.
8.5.1 A Sr'Spec® column is prepared by removing the bottom plug and the cap and
pressing the top frit snugly down to the resin surface using forceps (or glass rod).
The water is drained out, and the column is conditioned with 5 mL of 8 M
HNO3. The solutions are drained by gravity flow.
8.5.2 The sample solution is transferred to the reservoir of the column using a plastic
transfer pipet. Ideally, the volume of sample feed should be less than 10 mL.
Larger volumes can be used (up to about 30 mL), but at the risk of reduced
chemical recoveries. The column feed solution should be allowed to drain
completely before proceeding.
8.5.3 The sample container is rinsed with 3 mL of S M HNCK, which is then added to
the column.
8.5.4 The column is rinsed three times with 3 mL portions of 8 M HNO^ (each solution
is allowed to pass completely through before adding the next; the column
reservoir is rinsed well with each addition).
8.5.5 The end time of the last rinse is recorded to the nearest 15 min as the start of
ingrowth.
8.5.6 The Sr is eluted with 10 mL of 0.05 M HNO^ into a beaker or scintillation vial.
Chemical recovery is measured on this fraction by either a) evaporating and
weighing it, b) gamma counting the vial for ?5Sr, or c) removing a small aliquot.
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Laboraloiv/Radiochemistrv
diluting it to an appropriate volume, and measuring stable Sr by instrumental
means.
The spent column can be saved and reused for the same sample if the counting option chosen
involves later isolation and counting of90Y. If interferences from ~10Pb arc possible, the Pb can
be removed by passing 10 inL of 0.1 M through the column before reuse.
8.6 Preparation of Proportional Counter Source
A source prepared by this method can be used to measure gravimetric chemical recovery
and can be counted on any beta proportional counter. Reproducibility of counting
geometry is ± 1% if a dish with tapered sides is used. If instrumental analysis of stable Sr
is used for monitoring chemical yield, samples do not need to be weighed.
8.6.1 A clean counting dish is weighed to the nearest tenth of a milligram, and the tare
weight is recorded.
8.6.2 The counting dish is placed in the hood under a heat lamp.
8.6.3 The Sr eluate is evaporated onto the dish by adding small portions (2 to 3 mL) to
the dish and allowing each portion to evaporate to near dryness between
additions.
8.6.4 The dish is cooled and reweighed after all of the solution has evaporated. The
Sr(NO-), forms an easily weighed, nonhygroscopic solid that can be weighed to
0.1 mg.
8.6.5 The net residue weight is calculated by subtracting the tare weight of the
counting dish and the mass of extractant bleed (0.3 mg is the weight of crown
ether in 10 mL of eluate) from the weight of the dish plus residue.
8.6.6 The chemical recover)' is calculated by dividing the net residue weight by the
potential Sr(N03)0 in the sample (normally 10.0 mg from the carrier plus 2.42
limes the mg of ambient Sr in the sample).
8.7 Preparation of Liquid Scintillation Counter Source
A source prepared by this method can be used to measure gravimetric chemical recovery
and can be counted on any liquid scintillation counter. If instrumental analysis of stable
Sr is used for monitoring chemical yield, samples do not need to be weighed.
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DOE Method*
8.7.1 The sample should be collected in a weighed glass liquid-scintillation vial.
8.7.2 The vial is evaporated to dryness on a hotplate under a heat lamp.
8.7.3 The vial is cooled and reweighed. The Sr(N03), forms an easily weighed,
nonhygroscopic solid that can be weighed to 0.1 mg.
8.7.4 The net residue weight is calculated by subtracting the tare weight of the vial and
the mass of extractant "bleed" (0.3 mg is the weight of crown ether in 10 mL of
eluate) from the weight of the via! plus residue.
8.7.5 The chemical recovery is calculated by dividing the net residue weight by the
potential Sr(N03), in the sample (normally 10.0 mg from the carrier plus 2.42
times the mg of ambient Sr in the sample).
8.7.6 One milliliter of water is added to the vial, the residue is dissolved, and
scintillation cocktail is added.
8.8 Preparation of Cerenkov Counter Source
8.8.1 The vial containing the column strip solution can be used directly as the
Cerenkov counting vial.
8.9 Preparation of Pure wSr and Pure for Counter Calibration Sources
8.9.1 An appropriate volume of calibrated 90Sr standard solution should be measured
into a small beaker, an appropriate amount of Sr carrier should be added {e.g.,
1.00 mL, 10 mg Sr(N03).,}, and the solution should be evaporated to dryness.
The solution should be old enough so that the 90Y is in radioactive equilibrium
with its 90Sr parent.
8.9.2 The residue is dissolved in 3 mL of 2 M HN03.
8.9.3 A Sr*Spec® column is prepared as above. It should be conditioned for use by
passing 3 mL of 2 M HN03.
8.9.4 The dissolved residue is transferred to the column reservoir and the solution is
allowed to drain completely. The feedstock and subsequent rinses should be
retained.
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Laboraiorv/Radiochemistrv
8.9.4 The original beaker is rinsed twice more with 3 mL portions of 2 M HNOj,
adding each to the column and allowing it to drain completely before adding the
next.
8.9.5 The combined feed and rinses contain the 90Y from the original standard
solution. A counting source can be made from this solution by any appropriate
method, e.g., evaporation onto a planchet (with or without the addition of Sr
carrier) to produce a source for a proportional counter.
8.9.6 The 90Sr is eluted from the column with 10 mL of 0.05 M HN03. A counting
source can be made from this solution by any appropriate method, e.g.,
evaporation onto a planchet to produce a source for a proportional counter.
8.10 Suggested Counting Options
Detailed counting protocols are beyond the scope of this method. The type of
counting source made, the type of counter used, and the counting times and
frequencies will be dictated by the data quality objectives. Only general outlines
will be discussed. Of course, appropriate corrections must be made for
radioactive ingrowth and decay. Options involving more than one count will
generate two or more simultaneous equations that must be solved algebraically or
by the method of least squares.
8.10.1 If only 90Sr analysis is required, the Sr eluate can be evaporated to dryness and
then saved to allow ^°Y ingrowth. After sufficient ingrowth time (e.g., one
week) the residue is redissolved, and 90Y is purified as outlined in section 8.9
and counted.
This option can give very good detection limits and is independent of the
presence ofS9Sr. The column used for the original Sr purification can be reused
for this step if it is reconditioned by passing JO mL of 0.05 M HNO j and then
3 mL of2M HNO j through it just before reuse.
8.10.2 A scintillation counting source can be made and counted on a scintillation
spectrometer. By setting energy windows judiciously, ^Sr and ^^Sr can be
determined simultaneously using a single count immediately after purification.
This option has relatively poorer detection limits because of the generally higher
backgrounds associated with liquid scintillation counters, but is adequate for
many needs and gives very quick results. Measuring small amounts of90Sr in the
presence of large amounts ofs9Sr is difficult because of spectral overlap.
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DOE Methods
8.10.3 A proportional counter source can be made and counted on a low background
beta proportional counter. If 89Sr is known to be absent, a single count is
adequate to measure 90Sr. If the presence of 89Sr cannot be excluded, the first
count is the total of 89Sr and 90Sr, and the source must be recounted after a few
days (and preferably several times over the course of a few weeks) and the
ingrowth of 90Y and decay of 89Sr fitted mathematically.
This option can give veiy good detection limits. As in 8.10.2, measuring small
amounts of^Sr in the presence of large amounts of^Sr is difficult, this lime
because of the large counting interference from S9Sr. If a more precise measure
of^°Sr is needed, the residue on the plate can be redissolved and the 90Y isolated
and counted as in 8.10.1.
8.10.4 The eluate can be counted in a Cerenkov counter shortly after purification (to
measure 89Sr with little interference from 90Sr). The eluate can then be
evaporated and saved to allow ingrowth of 90Y. The 90Y is isolated as in 8.10.1
and counted in the Cerenkov counter with no interference from 89Sr. Alternately,
after the initial count, the column effluent can be recounted one or more times
during the ingrowth of 9®Y to allow calculation of the 9®Sr.
This option gives somewhat poorer detection limits because of the relatively
higher backgrounds associated with Cerenkov counting. It has tl\e advantages of
being fast and has virtually no counting inteiference between ^Sr and ^®Sr, even
at extreme ratios.
9.0 Calculations
Calculations are beyond the scope of this purification procedure and will be dictated by the
counting protocol used.
10.0 Quality Control
10.1 A method blank should be run with each sample set.
10.2 Precision and bias are determined using duplicate samples and matrix spikes.
11.0 Method Performance
11.1 Chemical yields are typically greater than 95% without preconcentration, greater than
90% with preconcentration by evaporation or cation exchange, and greater than 70% with
preconcentration by coprecipitation (limited by precipitation efficiency).
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LaboratonVRadiochemisiw
11.2 Separation from all expected interferences is greater than 99%, much greater for most
elements. If greater separation is needed, the column rinse volume can be increased (at
the risk of lowered Sr recovery) or the column eluate can be evaporated, redissolved, and
reprocessed through a second column (or a second lime through the same reconditioned
column).
11.3 Figure 1 summarizes the acid dependency of k' for alkalis, alkaline earths, actinides, and
other selected ions on Sr*Spec® resin.
11.4 Table 1 indicates the separation efficiencies obtainable with the Sr*Spec® resin.
12.0 Reference
Horowitz , E. P., R. Chiarizia, and M. L. Dietz. 1992. "A Novel Strontium-Selective Extraction
Chromatographic Resin." Solvent Exir. and Ion Exch., 10(2), pp. 313-336, 1992.
13.0 For More Information
Dietz, M. L., E. P. Horwitz, D. M. Nelson, and M. A. Wahlgren. 1991. "An Improved Method
for the Determination of 89Sr and 90Sr in Urine." Health Phys., Vol. 61, No. 6, pp. 871-877.
Nelson, D. M., M. A. Wahlgren, E. P. Horwitz, M. K. Dietz, and D. E. Fisher. 1990.
"Introduction of a Novel Method for Measuring 90Sr and 89Sr in Urine," in Proceedings of the
36th Annual Conference on Bioassay, Analytical, and Environmental Radiochemistry. Oak
Ridge, Tennessee.
7 997
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[HN03] M [HNO3] M
[HNO3] M [HNO3] M
Figure 1. Acid Dependency of k" for Various Ions at 23-25°C Sr-Spec®
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CALIBRATION OF THE LSC FOR DETERMINING GROSS ALPHA AND BETA ACTIVITIES
IN ACID DIGESTIONS OF SOIL AND SEDIMENT SAMPLES
1.0 PURPOSE
This procedure provides instructions for calibrating the liquid scintillation counter (LSC) used
to determining alpha and beta activities in soil and sediment samples by LSC counting.
2.0 SCOPE
This procedure is for calibrating the LSC used to determine alpha and beta activities in soil
and sediment samples by LSC counting. Due to the sample preparations sequences in this
procedure, an accurate determination of tritium is not feasible.
This method is used to measure the nitric acid-leachable portion of the soil and sediment
samples for alpha and beta radioactivity. Note that this is different than total alpha and beta
activities. Comparison of results with relevant action levels is the intended application for
this procedure. Results obtained from this procedure are not expected to be as accurate or
precise as detailed radiological separations and analyses.
This procedure provides instructions for calibrating the LSC that is used to analyze the
microwave acid digestion leachate of a soil sample for alpha and beta radioactivity. The
resulting leachate is mixed with LSC cocktail and counted on a Wallac 1415 with alpha/beta
discrimination. The instrument is calibrated for optimal discriminator setting, percent
misclassification vs. quench, percent counting efficiency vs. quench, and background count
rate vs. quench for both alpha and beta radioactivity using standards that are quenched with
a microwave digested soil leachate. Alpha and beta activity concentrations are determined by
applying misclassification and efficiency adjustments based on sample quench to the
instrument's count results.
If results from this screening method are considered significant based on applicable action
levels, then the sample should be analyzed by nuclide specific radioanalytical techniques.
5.0 TERMS/DEFINITIONS
1. Liquid scintillation counter (LSC) - Instrument that measures alpha and beta radioactivity
in a sample. The sample is mixed with LSC cocktail and the sample radioactivity interacts
with the cocktail producing light scintillation. The instrument measures the light
scintillations and converts them into a count rate. The Wallac 1415 with alpha beta
discrimination is the type of LSC that is used.
2. Liquid scintillation cocktail - Solution that contains a solvent and scintillator and
surfactant. Energy from radioactive decay events is transferred and converted into light
by the solution. The ready made Ultima Gold AB cocktail is used in this procedure.
3. Vortex/shaker - Device that shakes the LSC sample vial to ensure the cocktail is mixed
homogeneously with the sample.
4. Anti-static cloth - Cloth that removes static electricity that may be present on the LSC vial.
Static electricity may interfere with the ability of the LSC instrument to measure true
radioactivity accurately.
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5. Quenching - Interferences present in the sample that cause a reduction in the instrument
counting efficiency.
6. Transformed spectral index of the external standard (SQPE) - A value obtained by the
instrument that is used as an index of quenching in the sample and is based on the spectral
distribution of the external standard.
7. Optimal discriminator setting (ODS)- The Wallac 1415 uses the ODS to distinguish alpha
particle light pulses from beta particle light pulses. Alpha pulses are longer in duration
than beta pulses and the ODS is an adjustable timing mechanism where pulses longer than
the ODS are considered alpha and pulses shorter than the ODS are defined by the
instrument as beta.
8. Misclassification - When alpha pulses are defined by the instrument as beta (alpha
misclassification) or beta pulses are defined as alpha, misclassification has occurred.
Sample quenching is the main cause of misclassification. It is necessary to account for the
amount of misclassification that occurs in the sample in order to accurately quantify the
sample activity.
4.0 RESPONSIBILITIES
Laboratory Chemists/Technicians/Analysts are responsible for following this procedure, SRS
safety rules, and other written instructions from technical personnel and the laboratory
manager. They must assess if an operation is safe to continue and know how to follow the
proper channels to stop work, when appropriate. Laboratory personnel are to follow the
QA/QC protocol for all analytical operations and sample preparations. Vital sample
preparation and analytical data as directed by supervision must be recorded in bound
notebooks. Instrumentation used in the analysis and sample preparation must be calibrated,
and the calibration documented according to established frequency. Wastes generated from
this procedure must be characterized and disposed of properly from a regulatory and
environmental perspective.
5.0 PROCEDURE
EQUIPMENT AND SUPPLIES
- Liquid scintillation counter (Wallac 1415)
- Liquid scintillation cocktail with calibrated dispenser (Ultima Gold AB)
- Plastic liquid scintillation vials and caps (22 mL size)
- Vortex/shaker
- Anti-static cloth
- Calibrated alpha spike (24lAm used in this procedure)
- Calibrated beta spike (90Sr/°^Y used in this procedure)
- Computer with graphics/curve-fitting software
- Calibrated pipettes with disposable tips
- Quenching agent (Nitromethane, CH3NO2)
- IMHNO3
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MISCLASSIFICATION AND EFFICIENCY CALIBRATION
Optimal Discriminator Setting Setup
1. Prepare two standards, one pure alpha and one pure beta, in 1M HNO3 at approximately
1000 dpm/mL to determine the optimal discriminator setting (ODS) for the typical sample
matrix. If the sample:cocktail volume ratio is established at 4 mL:16 mL, then prepare the
standards with the same ratio.
2. Add 1 mL of alpha spike activity to a plastic vial. Add additional 1M HNO3 to total 4 mL
of sample.
3. Working within the confines of an acid hood, add 16 mL of Ultima Gold into the vial.
4. Ensure the cap is fitted tightly on the vial and place the vial on the vortex/shaker for ten
seconds or manually shake vigorously. Label the standard on the cap.
5. Repeat steps 2-4, but add 1 mL of beta spike activity in place of the alpha spike. Wipe both
standards thoroughly with the anti-static cloth.
6. Count the beta standard first and then the alpha standard using the programmed
alpha/beta standards protocol. The count time should be long enough so that the
standard deviation of the observed counts is 5% or less.
7. The instrument sets the optimal discriminator setting based on the series of iterative alpha
counts and beta counts performed on each alpha and beta standard, respectively.
Quenched Standard? Preparation and Counting
1. Add 1 mL alpha spike to each standard. Add varying amounts of a quenching agent such
as nitromethane (10 - 200 jiL) and 1M HNO3 to each standard for a total of 4mL sample
volume. The spike activity should be sufficient to produce 10,000 counts in a reasonable
amount of time. The resulting range in the quench value (SQPE) should be approximately
800 to 600.
2. Repeat step 2 but use the beta spike in place of the alpha spike.
3. Add 16 mL of Ultima Gold AB cocktail to each standard vial. Cap tightly and shake
manually or by using the vortex/shaker. Wipe each vial with the anti-static cloth.
4. Count each series of standards using a counting protocol set at the optimal discriminator
setting previously determined. Suggested window settings for the protocol based on
using 241 Am and 50sr/90y as the alpha and beta standards, respectively are:
Alpha: 90-500 Beta: 50-1000
5. Each standard should be counted long enough so that the standard deviation of the
observed counts is 5% or less.
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Background Sample Preparation and Counting
1. Add different amounts (10 - 200 nL) of the quenching agent nitromethane to LSC vials to
prepare a series of background samples that vary over the quench range of typical sample
preparations (approximately 800 to 600 SQPE)
2. Add amounts of 1M HNO3 to each vial so that the final sample volume is 4 mL.
3. Add 16 mL of Ultima Gold AB cocktail to each vial. Cap the vial tightly and shake
manually or by using the vortex/shaker. Wipe each vial with the anti-static cloth.
4. Count the series of background standards using the same counting program as the
quenched standards with the optimal discriminator setting previously determined.
Suggested window settings for the protocol based on using 241 Am and 90gr/90Y as the
alpha and beta standards, respectively are:
Alpha: 90-500 Beta: 50-1000
5. Each background standard should be counted for 1 hour.
Developing Percent Misclassification vs. Quench Curves
1. After the series of alpha standards have been counted, determine the percent
misclassification of alpha activity as beta activity for each standard by using the following
formula:
[B0 4- (A0 + B0) ] x 100 = percent misclassification of alpha activity as beta activity (X^)
2. After the series of beta standards have been counted, determine the percent
misclassification of beta activity as alpha activity for each standard by using the following
formula:
[A0 -s- (A0 + B0) ] x 100 = percent misclassification of beta activity as alpha activity (Xp)
where,
A0 = Alpha count rate in the alpha channel
Bo = Beta count rate in the beta channel
3. Create an X-Y scatter plot of the percent alpha misclassification vs. quench data using a
spreadsheet program with capabilities of curve-fitting data.
4. Generate a curve-fitted equation of the data where the dependent variable (Y) is percent
alpha misclassification and the independent variable (X) is the quench value.
5. Using percent beta misclassification as the dependent variable, perform steps 3 and 4
again.
6. Now the percent misclassification for alpha activity and beta activity can be determined by
measuring the quench value in a sample from these empirical relationships.
-------
Developing Percent Efficiency vs. Quench Curves
1. After the same series of alpha standards used for the alpha misclassification calculations
have counted, determine the percent alpha efficiency for each standard by using the
following formula:
[(A0 + B0) -5- As] x 100 = Percent alpha efficiency
where,
As = Known alpha activity added to the standard
2. After the same series of beta standards used for the beta misclassification calculations have
counted, determine the percent beta efficiency for each standard by using the following
formula:
[(Ao + B0) -*¦ B$] x 100 = Percent beta efficiency
where,
Bs = Known beta activity added to the standard
3. Create an X-Y scatter plot of the percent alpha efficiency vs. quench data using a
spreadsheet program with capabilities of curve-fitting data.
4. Generate a curve-fitted equation of the data where the dependent variable (Y) is percent
alpha percent efficiency and the independent variable (X) is the quench value.
5. Using percent beta efficiency as the dependent variable, perform steps 3 and 4 again.
6. Now the percent counting efficiency for alpha activity and beta activity can be determined
by measuring the quench value in a sample from these empirical relationships.
NOTE: The calibration curves established are sensitive to changes in parameters such as:
- the type of'quenching agent
- the type of LSC cocktail
- the radionuclide used as the spike
- the type of vial used (plastic vs. glass)
If these parameters are changed for sample analyses, it is recommended that calibration
curves be developed using the same parameters for sample analyses. It is also recommended
that standards be counted within 48 hours of preparation to minimize the effect which the
acidic sample solution has on the cocktail performance.
-------
6.0 REFERENCES
Wong, R., Burnett W. C., and Clark S. B., 1997, Development of an improved assay for the
determination of gross alpha and beta concentrations in soil by liquid scintillation counting
(abs.), Proceedings, 43rd Annual Conference on Bioassay, Analytical, and Environmental
Radiochemistry; Charleston, SC, Nov. 9-13,1997.
Burnett, W. C., Wong, R., Clark S. B., and Crandall, B., 1998, Direct counting of soil wafers - an
improved total alpha/beta screening analysis, Journal of Radioanalytical and Nuclear
Chemistry, in press.
Packard Instrument Company, 1989, Liquid scintillation analysis - Science and technology,
Packard Instrument Company, Inc.
Environmental Monitoring Section, 1997, Microwave acid digestion of soil and sediment
samples - WSRC-3Q1-4 Procedure 2900, Westinghouse Savannah River Company.
Passo, C. J. and Cook, G. T., 1994, Handbook of environmental liquid scintillation
spectrometry - A compilation of theory and methods, Packard Instrument Company.
-------
GROSS ALPHA AND BETA ACTIVITIES IN SOIL, SEDIMENT, AND WATER SAMPLES
1.0 PURPOSE
This procedure provides instructions for counting soil and sediment samples that have been
prepared via the Hot Block acid digestion technique. Calculations for the alpha and beta
radioactivity concentrations present in the acid leachable portion of the samples are also
provided.
2.0 SCOPE
This procedure is for counting LSC microwave acid digested samples and calculating the total
alpha and beta radioactivity present in the acid leachate. Due to the sample preparation
sequences used, the accurate determination of tritium is not feasible.
This method is used to measure the nitric acid-leachable portion of the soil and sediment
samples for alpha and beta radioactivity. Comparison of results with relevant action levels is
the intended application for this procedure. Results obtained from this procedure are not
expected to be as accurate or precise as detailed radiological separations and analyses.
This procedure provides instructions for counting the microwave acid digestion leachate of a
soil sample using an LSC and quantifying the alpha and beta radioactivity in the leachate.
The instrument (Wallac 1415) is calibrated for optimal discriminator setting, percent
misclassification vs. quench, percent counting efficiency vs. quench, and background count
rate vs. quench for both alpha and beta radioactivity using standards that are quenched with
nitromethane (see additional protocol). Alpha and beta activity concentrations are
determined by applying misclassification and efficiency adjustments based on sample quench
to the instrument's count results.
If results from this screening method are considered significant based on applicable action
levels, then the sample should be analyzed by additional nuclide specific radioanalytical
techniques.
3.0 TERMS/DEFINITIONS
1. Liquid scintillation counter (LSC) - Instrument that measures alpha and beta radioactivity
in a sample. The sample is mixed with LSC cocktail and the sample radioactivity interacts
with the cocktail producing light scintillation. The instrument measures the light
scintillations and converts them into a count rate. The Wallac 1415 with alpha/beta
discrimination is the type of LSC that is used.
2. Quenching - Interferences present in the sample that cause a reduction in the instrument
counting efficiency.
3. Transformed spectral index of the external standard (SQPE) - A value obtained by the
instrument that is used as an index of quenching in the sample and is based on the spectral
distribution of the external standard.
4. Optimal discriminator setting (ODS)- The Wallac 1415 uses the ODS to distinguish alpha
particle light pulses from beta particle light pulses. Alpha pulses are longer in duration
than beta pulses and the ODS is an adjustable timing mechanism where pulses longer than
-------
the ODS are considered alpha and pulses shorter than the ODS are defined by the
instrument as beta.
5. Misclassification - When alpha pulses are defined by the instrument as beta (alpha
misclassification) or beta pulses are defined as alpha, misclassification has occurred.
Sample quenching is the main cause of misclassification. It is necessary to account for the
amount of misclassification that occurs in the sample in order to accurately quantify the
sample activity.
4.0 RESPONSIBILITIES
Laboratory Chemists/Technicians/Analysts are responsible for following this procedure, FSU
safety rules, and other written instructions from technical personnel and the laboratory
manager. They must assess if an operation is safe to continue and know how to follow the
proper channels to stop work, when appropriate. Laboratory personnel are to follow the
QA/QC protocol for all analytical operations and sample preparations. Vital sample
preparation and analytical data as directed by supervision must be recorded in bound
notebooks. Instrumentation used in the analysis and sample preparation must be calibrated,
and the calibration documented according to established frequency. Wastes generated from
this procedure must be characterized and disposed of properly from a regulatory and
environmental perspective.
5.0 PROCEDURE
EQUIPMENT
- Liquid scintillation counter (Wallac 1415)
- Computer with statistics software for performing calculations of activity concentrations
- Anti-static cloth
COUNTING OF SAMPLES
1. Perform the Hot Block acid digestion procedure (see separate protocol) on the soil or
sediment samples. One-liter filtered water samples are preserved with HN03 to pH = 1-2,
evaporated to dryness and picked up in 4M HN03. The treatment from that point on is
the same as for soils.
2. Count the samples using a counting program that utilizes the optimal discriminator
setting previously and the suggested window settings defined from the calibration
protocol.
3. Wipe the sample vials with anti-static cloth and place the samples into the sample carrier.
4. Place the sample carrier on the right side in the LSC and start the count. Suggested count
time is 20 minutes for each sample.
5. Use these count data to determine the alpha and beta concentrations in the soil described
by the next section.
-------
CALCULATION OF ALPHA AND BF.TA CONCENTRATIONS IN SOIL
1. The net alpha and beta count rates have to be adjusted for "misclassification."
Misclassification occurs when true alpha counts cross over into the beta channel and are
misidentified as beta counts. Conversely, beta counts can cross over into the alpha
channel and will be misidentified as alpha counts. Use the misclassification vs. quench
curves that were previously developed in the calibration procedures with the statistical
computer software to determine the alpha misclassification and beta misclassification
values for the measured sample quench (SQPE value).
2. The net alpha and beta count rates have to be adjusted for changes in efficiency due to
sample quench. Detector efficiency changes as a function of sample quench for alpha and
beta radioactivity. Use the efficiency vs. quench curves that were previously developed in
the calibration procedures with statistical computer software to determine the alpha
efficiency and beta efficiency values for the measured sample quench (SQPE value).
2. The alpha activity concentration (At) is described by the following equation:
A, (dpm / g) = tA,-At)-(A,-Ab).X,-(B,-Bt).X,
(l-Xp -XJ*Acff *(mass)
where,
Ag = Gross alpha count rate
Ab = Alpha background count rate
Bg = Gross beta count rate
Bb = Beta background count rate
Xa = Alpha crosstalk
Xp = Beta crosstalk
Aeff = Alpha efficiency
mass = sample mass in grams
3. The beta activity concentration (Bt) is described by the following equation:
B, (dpm / g):
(B?-Bb)-(BE-Bb)*Xc-(Ag-Ab)*Xc
(l-X/j -Xa)*Beff*(mass)
where,
Beff = Beta efficiency
4. The alpha 1 sigma counting error (Aerr in dpm/g) is described by the following equation:
-------
*v
where,
Tg = Sample count time in minutes
Tb - Background count time in minutes
The beta 1 sigma counting error (Berr in dpm/g) is described by the following equation:
*X 2
'v a
NOTE: The calibration curves established are sensitive to changes in parameters such as:
- the type of soil
- the type of LSC cocktail
- the radionuclide used as the spike
- the type of vial used (plastic vs. glass)
It is recommended that samples be counted within 48 hours of preparation to
minimize the effect which the acidic sample solution has on the cocktail performance.
6.0 REFERENCES
Wong, R., Burnett W. C., and Clark S. B., 1997, Development of an improved assay for the
determination of gross alpha and beta concentrations in soil by liquid scintillation counting
(abs.), Proceedings, 43rd Annual Conference on Bioassay, Analytical, and Environmental
Radiochemistry; Charleston, SC, Nov. 9-13,1997.
Burnett, W. C., Wong, R., Clark S. B., and Crandall, B., 1998, Direct counting of soil wafers - an
improved total alpha/beta screening analysis, Journal of Radioanalytical and Nuclear
Chemistry, in press.
Packard Instrument Company, 1989, Liquid scintillation analysis - Science and technology,
Packard Instrument Company, Inc.
Environmental Monitoring Section, 1997, Microwave acid digestion of soil and sediment
samples - WSRC-3Q1-4 Procedure 2900, Westinghouse Savannah River Company.
Passo, C.}. and Cook, G. T., 1994, Handbook of environmental liquid scintillation
spectrometry - A compilation of theory and methods, Packard Instrument Company.
K
+ A>
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-------
GAMMA SPECTROMETRIC ANALYSIS OF SOILS AND SEDIMENTS
1.0 PURPOSE
This procedure provides instructions for the routine analysis of y-emitting
nuclides in soils and sediments. The procedure follows that detailed in the
EML HASL-300 Procedures Manual (pages 4.5-17 to 4.5-27) which is attached.
2.0 SCOPE
This procedure is for analysis of soil and sediment samples for 7-emitting
radionuclides. The nuclides which will be quantified and the estimated
detection limits are as follows:
Nuclide
Energy
MDA's
keV
(PCi/g)
Pb-210
45.6
0.191
Am-241
59.6
0.006
U-238
63.2
0.241
(Th-234)
U-235
143.8
0.013
Pb-214
295.0
0.033
Ac-228
338.4
0.031
Pb-214
351.9
0.019
Th-208
583.1
0.033
Cs-134
604.7
0.007
Bi-214
609.3
0.033
Cs-127
661.6
0.007
Bi-214
1120.2
0.039
Co-60
1173.2
0.013
Co-60
1332.5
0.010
K-40
1460.1
0.233
The MDA's that are listed are based on 16-hour count times, our standard
geometry using 100-cc aluminum cans (same as EML), and recently-
determined efficiencies and backgrounds for our Ortec intrinsic germanium
detector with a beryllium window. The MDA's were calculated using the
standard Currie equation.
See attached documentation from the EML Manual as well as a description of
-------
An Improvement for a Relative Self-Absorption Correction for Intrinsic Germanium
Detectors'
lave Young and Bill Burnett Environmental Radioactivity Measurement Facility, Department of
Oceanography, Florida State University, Tallahassee, Florida 32306 (Tel: 904-644-6703; Fax: 904-644-2581;
email: wbumett@mailer.fsu.edu);
and
Wilbur Sigmon and James Westmoreland Environmental Physics, Inc., General Engineering
Laboratories, P.O. Box 30712, Charleston, South Carolina 29417
Gamma ray spectrometry provides a simple, nondestructive means to analyze
specific radionuclide activities in soils and sediments. However, since lower energy y-
rays have less penetrating ability than higher energy photons, they tend to interact
more readily with matter. Unless properly accounted for, sample self-absorption will
reflect an activity for the absorbed nuclide that is lower than the true activity. An
accurate measurement of the absolute efficiency of an intrinsic germanium detector is
also dependent on the correction of this self-absorption. Measurements of the efficiency
using higher density standards will reflect a lower apparent efficiency, and likewise,
lower density standards will reflect a higher apparent efficiency.
A method described by Cutshall et al. (1983) requires the use of direct transmission
measurements on each sample using an external source. However, individual direct
transmission measurements can be a limiting factor in sample throughput for a
laboratory interested in processing large quantities of samples. A simplified method for
correcting self-absorption in sample sets containing a wide variety of weights can be
devised by relating the absorption correction. ^Vo) as a function of gamma energy
(keV):
(l '1
where:
A = final, corrected activity (dpm/g);
0 = uncorrected activity (dpm/g);
T = beam intensity through the sample; and
1 = beam intensity through the efficiency standard.
In our case, the beam intensities are taken as the direct transmission measurements of a
mixed nuclide external source through the sample (T) and the efficiency standard (I).
By curve fitting plots of the self-absorption correction versus energy for many samples,
the following equation can be developed:
y = a ln(x) + b
For presentation at the Conference on Bioassay, Analytical, and Environmental Radiocherrustry"
-------
where y is A/O (absorption factor), x is the energy (keV), and 'a' and 'b' are coefficients
that relate to sample weight. These coefficients 'a' and 'b' can be obtained from each
curve fit of -^/O versus energy. An example of such a fit is shown in Figure 1. When
each coefficient is plotted independently against sample weight, the relationship
between the coefficients and sample weight is such that future determination of these
coefficients requires only knowledge of the sample weight. Thus, from these
interpolated coefficients a self-absorption factor can be derived for any energy.
1.40 t,
O
<
1.30-
1.20-
VI.
y = 1.692x'a059
r2 = 0.969
i ,
1.10-
¦¦»...
x
1.00.
500
1000
1500
2000
Energy (keV)
Figure 1: An example of the self-absorption correction factor (^-/o) versus y-ray energy
(keV) for one soil sample. A mixed-nuclide external source was used to make
transmision measurements through the sample.
The use of a single geometry for all samples and standards allows the sample
weight to be used as a proxy for sample density. Strictly speaking, the weight is not
solely dependent upon density because of sample specific differences in grain size,
shape, packing density, etc., although these differences may be small for similar samples
(Burnett et al., 1993). An example of how an estimate of ^/q versus sample weight for
one energy (234Th at 63.3 keV) shows that sample weight can provide a fairly good
-------
Weight (g)
Figure 2: The self-absorption factor (-^/o) versus sample weight (g) for 75 samples
analyzed by Florida State University.
The elimination of direct transmission measurements through samples and
efficiency standards greatly improves the ability of laboratories to analyze large
quantities of samples. By simply using the historical data available in the laboratory
from previously run samples, this self-absorption correction can be developed and
incorporated into existing calculation software.
References
Burnett, W. C., C. D. Hull, J. E. Young, and P. H. Cable. 1993. A Simple Self-Absorption
Correction for Gamma-ray Counting of Soils and Sediments. 39^ Annual
Conference on Bioassay, Analytical, and Environmental Radiochemistry, Colorado
Springs, CO, October 11-15,1993.
Cutshall, N. H., I. L. Larsen, and C. R. Olsen. 1983. Direct analysis of in sediment
samples: self-absorption corrections. Nuclear Instruments and Methods 206: 309-
-------
An Improvement for a Relative Self-Absorption
Correction for Intrinsic Germanium Detectors
Jaye Young and Bill Burnett
Department of Oceanography
Florida State University
Tallahassee, Florida 32306
and
James Westmoreland and Wil Sigmon
Environmental Physics, Inc.
General Engineering Laboratories
Charleston, South Carolina 29417
-------
Bioassay '94
Statement of the Problem
• correction for y-ray self-absorption by samples can be
important in analysis of radionuclides in soils and
sediments, especially at low energies
• direct transmission measurements provide an excellent
method for a relative self-absorption correction
• however, direct transmission measurements may be a
limiting factor in sample throughput
-------
Approach
• select a group of samples to provide a large
range in sample weignts
• make direct transmission measurements
• compile observed data for the relationship
between absorption and energy for any
sample weight
-------
assay
Direct Transmission Correction
Sealed External
Source
Pb-210, U-238, Ra-226
y-rays pass through sample giving a direct
measurement of absorption.
-------
Bioassay *94 m —
Absorption Correction versus
Sample Weight
Weight (g)
-------
Bioassay '94
Absorption Factor
Calculation
Where: A=corrected activity; 0=uncorrected;
T=attenuated count rate; and
I=unattenuated count rate.
-------
Bioassay '94
Absorption Factor versus Energy
1.6
1.4-
1.2-
o
^ 1.0
0.8-
0.6
1 ~
Chilean Phosphorite Rock (193.14g)
y = -0.200LOG(x) + 1.642 r2 = 0.751
Q ~ ~
0
500 1000 1500
Energy (keV)
2000
Florida State University
-------
Bio assay '94
Relationship between Energy
and Sample Weight
y = a (log x) + b
where:
y = absorption factor (A/O);
x = energy (keV); and
a & b = coefficients
-------
Coefficient 'a' versus Sample Weight
0.2
0.1
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C
O
u -o.i
"ra
-0.2
-0.3
0 50 100 150 200 250
Weight (g)
Florida State University
y = -0.00239(±1.88E-4)x + 0.347(±0.0456)
r2 = 0.749 n=56
© Environmental Physics Inc
-------
Bioassay '94 -
Coefficient 'b' versus Sample Weight
Weight (g)
BB
-------
Bioassay '94
Baltic Sea Sediment
126.34 g
Pb-210
U-238
Ra-226
Cs-137
-------
Bioassay '94
Indonesian Stream Sediment
76.28 g
70
60-
50-
40-
30-
20-
10-
0
IAEA-314
T
illli!
Ill#
I , - ,*4 , * ».
Siiiill
U-238
Certified
Modeled
Direct Transmission
Ra-226
-------
Bioassay '94
Irish Sea Sediment
132.39 g
80
7s 60-j
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40'
p
U
<
20-
0-
IAEA-135
B Certified
H Modeled
I _ » < J T ijf
^ U ^
Am-241
Cs-137
-------
Conclusions
Direct transmission measurements make
excellent absorption corrections for soils and
sediments.
• These absorption corrections are limited to the
radionuclides available in an external source.
A model to relate the self-absorption to energy
can allow one to obtain corrected activities for
any radionuclide in the sample.
• Future work should focus on extending the model
to extreme sample densities.
saa
-------
4.5.2.3
GAMMA
Contact Person: Colin G. Sanderson
APPLICATION
This procedure Is used for the nondestructive measurement of 7-ray emitting
radionuclides from a variety of environmental matrices by high resolution germanium
(Ge) detector 7-rav spectrometry and Nal(Tl) detector 7-rav spectrometry. It is
applicable to nuclides emitting 7-rays with energies > 20 keV for Ge detectors and 50
keV for NaJ(Tl! detectors. For typical counting systems and sample types, activity levels
of about 40 Bq are easily measured and sensitivities as low as .002 Bq can be achieved
for many nuclides. Count rates in excess of 2000 cps should be avoided because of
electronic limitations. High count rate samples can be accommodated by dilution or by
Increasing the sample to detector distance.
The procedure is used for either qualitative, quantitative or relative determinations.
In tracer -work, the results may be expressed by comparison with an initial concentra-
tion of a given nuclide which is taken as 100%. For radioassay, the results may be
expressed in terms of known standards for the radionuclides known to be present. In
addition to the quantitative measurement of 7-ray radioactivity, 7-ray spectrometry can
be used for the identification of specific 7 emitters in a mixture of radionuclides.
Genera] information on radioactivity ana the measurement of radiation has been
published. Information on the specific application of 7-ray spectrometry is also
available in the literature.
DESCRIPTION OF THE SYSTEM
Gamma-ray spectra are measured at EML with modular equipment consisting of a
detector, an amplifier, a pulse-height analyzer, memory, and a permanent data storage
device. Lithium-drifted germanium. Ge(Li), or high purity Ge detectors (p-type or
n-type) are used for the analysis of complex 7-ray spectra because of their excellent
energy resolutions. Tnese Ge detectors, however, are characterized by high cost and
require cooling with liquid nitrogen. TnalJium activated sodium-lodiae crystals. Nai(Tl),
can be operated at ambient temperatures ana are ofien used at EML as 7-ray detectors
Environ,Tie-i M^2sure~en',s Labo.-a'.ory
U.S Depatne-', o( Energy
4.5-17
-------
In spectrometer systems. However, their energy resolutions limit their use to the
analysis of single nuclides or simple mixtures of a few nuclides.
Upon completion of the 7-ray assay, the spectral data are interpreted and reduced
to nuclide activity of Bq (disintegrations per second) or related units suited to the
particular application. At this time, the spectral data may be inspected on the CRT to
identify the 7-rav emitters present. This Is accomplished by reading the channel
number from the x-axls and converting to 7-ray energy by multiplying by the
appropriate keV/channel (system gain). IT the system Is calibrated for 1 kcV per
channel with channel zero representing 0 keV. the energy will be equal to the channel
number. The channel number or 7-ray energy in kcV is usually displayed on the CRT.
Identification of nuclides is aided by catalogs of 7-ray spectra and other nuclear data
tabulations. Because of the reduced spectral resolution obtained with h'aHTl) detectors,
this technique can only be applied to samples of single nuclides or very simple
combinations of nuclides.
Data reduction of spectra taken with Ge spectrometry systems is usually
accomplished by integration of the photopeaks above a definable background (or
baseline), and by subsequent activity calculations using a library that Includes data
such as nuclide name, half-life, 7-ray energies and associated abundance (intensity or
branching ratios). Computer programs for data reduction of Nal(Tl) detector data have
been used extensively at EML. Data reduction of spectra Involving mixtures of nuclides
Is usually accomplished by least-square fitting routines to a library of standard spectra
of the individual nuclides acquired under individual conditions.
Variation of the physical geometry of the sample and its relationship with the
detector will produce both qualitative and quantitative variations in the 7-ray spectrum.
To adequately account for these geometry effects, calibrations are designed to duplicate
all sample counting conditions including source-to-detector distance, sample shape and
size.
Electronic problems, such as erroneous deadtime correction, loss of resolution,
ana random summing, may be avoided by keeping the gross count rate below 20-00 cps'
and also by keeping the Geaatime of the analyzer below 5%. Total counting time is
governed by the radioactivity of the sample, the detector-to-source distance, and the
acceptable Polsson counting uncertainty.
In complex mixtures of 7-ray emitters, the degree of interference of one nuclide In
the determination of another Is governed by several factors. If the 7-ray emission rates
from different radionuclides are similar. Interference will occur when the photopeaks
are not completely resolved ana overlap. If the nuclides are present in the mixture at
markedly different levels of activity, nuclides of higher 7 energies that are predominant
can cause serious Interferences with the interpretation of minor, less energetic, 7-ray
Env.rormsnlsJ W.MS'jrs.Tte-s Uix>r33iv
-------
photopeaks. The complexity of the analysis method Is due to the resolution of these
interferences and, thus, one of the main reasons for computerized systems.
Cascade summing may occur when nuclides thai decay by a 7-ray cascade are
analyzed. Cobalt-60 is an example; 1172 and 1333 keV 7-rays from the same decay
may enter the detector to produce a sum peak at 2505 keV or a count In the continuum
between the individual peaks and the sum peak: thus, causing the loss of counts from
one or both of the other two peaks. Cascade summing may be reduced by increasing
the source to detector distance. Summing is more significant If a well-type detector Is
used.
Random summing is a function of counting rate and occurs in all measurements.
The random summing rate is proportional to the total count squared and the resolving
time of the detection system. For most systems, random summing losses can be held to
< 1% by limiting the total counting rate to 1000 cps.
The density of the sample is another factor that can affect quantitative results.
Errors from this source can be avoided by preparing the standards for calibration in
solutions or other matrices with a density comparable to the sample being analyzed.
Another approach Is to apply attenuation corrections to all calibration standards and
samples based on sample weight, known volume. 7-ray path length arid average atomic
number of the sample matrix.
APPARATUS
A 7-ray spectrometer consists of the following components:
A. Detector assembly.
1. Germanium detector - Tne detector should have a volume of at least 50 cm'^, with
a full width at one half the peak maximum (rWHM) < 2.2 keV at 1332 keV,
certified by the manufacturer. A charge-sensitive preamplifier using low noise field
effect transistors should be an integral pan of the detector assembly. A convenient
support should be provided for samples of the desired form. Vertical systems allow
the standard/sample to be placed directly on the detector end cap.
2. NaI(Tl) detector - Tne sodium iodide crystal, activated with about 0.1 percent
thallium iodide, should contain <5 vg g" ^ of K and should be free of other
radioactive materials. Tne crystal should be attached and optically coupled to a
multiplier phototube. (Tne multiplier phototube requires a preamplifier or a
cathode follower compatible preamplifier with the amplifier.) The resolution
IFNVKM) of the assembly for the photopeak of ^7Cs should be < 7 % for 2 75 mm
by 75 mm detector.
Environmental Measurements Uborsiory
U.S. Departnen; o! Energy
4.5-19
-------
3. Shield - The detector assembly should be surrounded by an external radiation
shield made of massive metal, equivalent to 102 mm of Pb In 7-ray attenuation
capability. It is desirable that the inner walls of tbe shield be at least 127 mm In
distance from the detector surfaces to reduce backscatter. If the shield is made of
Pb or a Pb liner, the shield must have a graded Inner shield of 1.6 mm of Cd or tin
lined with 0.4 mm of copper, to attenuate the 88 keV Pb rays. The shield must
also have a door or port for inserting and removing samples.
4. High-voltage power/bias supply - The bias supply required for Ge detectors usually
provides a voltage up to 5000 V and 1 to 100 uA. Nal(Tl) detectors require a hlgh-
voltagc power supply of a range of usually from 500 to 3000 v and up to 10 mA to
operate the multiplier phototube. The power supply should be regulated to 0.1%
with a ripple of not more than 0.01%. Line noise caused by other equipment
should be removed with filters and additional regulators.
5. Amplifier - A spectroscopy amplifier compatible with the preamplifier and with the
pulse-height analyser should be used.
B. Data acquisition and storage equipment.
1. Data acquisition - A multichannel pulse-height analyzer (MCA) or stand-alone
analog-to-digital converter (ADC) under software control of a separate computer,
performs many functions that are required for 7-ray spectrometry. An MCA or
computer collects the data, provides a visual display, and outputs final results or
raw data for later analysis. The four major components of an MCA are the ADC.
the memory, control, and input/output. Tne ADC digitizes the analog pulses from
the detector amplifier. Tne magnitude of these pulses is proportional to the energy
of the photon deposited in the detector. Tne digital result is used by the MCA to
select a memory location (channel number) which is used to store the number of
events which have occurred with that energy. Simple data analysis ana control of
the MCA Is accomplished with microprocessors. Tnese processors control the
Input/output, channel summing over set regions of interest, and system energy
calibration, etc.
2. Data storage - Because of the use of microprocessors, modem MCAs provide a
wide range of input ana output (I/O) capabilities. Typically, these capabilities
include the ability to transfer any section of data to one or more of the following:
terminal, hne printer, cassette tape, floppy or hard disk, X-Y plotter, ana to
computer Interfaces via a serial or parallel port.
Ncvembe-
4.5-20
Environment Measurement L3bors'oiy
-------
SAMPLE/STANDARD CONTAINERS
Sample mounts 2nd containers must have a convenient reproducible geometry.
Considerations include commercial availability, case of use and disposal, and the
containment of radioactivity for protection of the personnel and working environment
from contamination. The evaporation of liquid samples to dryness is not necessary and
liquid samples up to 1 L may be used. Massive samples may cause significant self-
absorption oflow energy 7-rays and may degrade the higher energy 7-rays. A /3
absorber consisting of about 6 mm of Al. Be. or plastic may be used for samples that
have a significant 0 activity and high p energies.
CALIBRATION AND STANDARDIZATION
This section describes the analysis of mixtures of radionuclides with Ge detectors
or single or simple mixtures of radionuclides with Nal(Tl) detectors. If complex mixtures
of radionuclides are to be analyzed with Nal(Tl) detectors, refer to page 4.5-19.
A. Preparation of apparatus.
Follow the manufacturer's instructions, limitations, and cautions for the setup and
the preliminary testing of all of the spectrometry equipment to be used in the analysis.
This equipment would include, as applicable: detector, power supplies, preamplifiers,
amplifiers, multichannel analyzers, ana computing systems.
Place an appropriate volume of a standard or a mixed standard of radionuclides in
a sealed container and place the container at a desirable ana reproducible source-to-
aetector distance. For environmental analysis, mosi standards/samples are counted 21
the detector end cap. The standard should pro\nae about 100 cps in the peaks of
interest and should be made up of standard sources traceable to a nationally certified
laboratory. In all radionuclide measurements, the volumes, shape, physical and
chemical characteristics of the samples, standards and their containers must be as
Identical as practicable for the most accurate results.
B. Energy calibration.
Tne energy calibration (channel number of the multichannel analyzer versus the 7-
ray energy) of the detector system is accomplished at a fixed gain using standards
containing known radionuclides. Tne standards should be in sealed containers and
should emit at least four different 7*-ray energies covering the range of interest, usually
50 keV to 2000 keV in order to test for system linearity. Some commercially available
nuclides suitable for energy calibration are: 210Pb, 46.5 keV; 241Am. 59.5 keV; 109Cd.
88 keV; 141Ce. 145 keV; 51Cr. 320 keV; 137Cs. 662 keV; 54Mg. 835 keV; 22Na. 511
and 1275 keV; , 89S and 1836 keV; ^Co. 1173 ana 1332 keV; eoulbbratea 22®Ra.
Environment Wsasu'c-Tienls L2bo;21ory
U S Deperrrienj c! Energy
4.5-21
-------
186. 352. 609. 1 120, and 1765 kcV. A mixed 7-ray standard for energy and efficiency
calibration is also commercially available. This standard can be obtained In solid form
in a user supplied container. The radionuclide purity of the standards should be
verified periodically to ensure against accidental contamination or the presence of long-
lived impurities by comparing the observed spectra with the spectra published In the
literature.
A multichannel analyzer should be calibrated to cover the range of interest. If the
range is 50 to 2000 keV. the gain of the system should be adjusted until the 1^7Cs
photopeak. 662 keV, is about one-third full scale. Leaving the gain constant, locate at
least three other pholopeaks of dliTerent energies, covering the same range. Determine
and record the multichannel analyzer channel number corresponding to the maximum
count rate for each of the four 7 energies. Germanium detectors will have a linear
relationship If the equipment is operating properly. Similarly, multichannel analyzers
and Nal(T]) detectors being produced today are capable of producing an almost linear
energy response. Samples should not be analyzed if this relationship Is not obtained.
Follow the appropriate manufacturer Input instructions for the determination of the
slope and intercept. During each day in which the spectrometry system is being used
to analyze samples, the above sequence of operation shall be repeated using at least two
different 7 energies. If the slope and intercept are essentially unchanged, the energy
calibration data remain valid. If an appreciable change In the slope or intercept Is
evident, the entire calibration procedure must be rerun.
C. Photon detection efficiency calibration.
Accumulate an energy spectrum using sealed, calibrated radioactivity standards In
a desired and reproducible counting geometry. At least 10.000 net counts (total counts
minus the compton continuum and ambient background) should be accumulated in
each full-energy 7-ray peak of interest.
Correct the radioactivity standard source 7-ray emission rate for the decay from
the time of standardization to the time at which the count rate is measured.
Calculate the full-energy peak efficiency Ef as follows:
Ef = Np/Ng
where
Ef = full-energy peak efficiency (counts per 7-ray emitted),
Np = net 7-ray count In the full-energy peak of interest (cps). and
Kg = 7-ray emission rate (7 rays sec"1).
Nove.Tits: 1S?0
4.5-22
Environmental MaasurerrwnE Lsborsory
-------
If the standard source Is calibrated 2s to activity, the 7-rav emission rale Is given by:
Ng = A'Pg
where
A = number of nuclear decays per second, and
Pg = probability per nuclear decay for the 7 ray.
For Ge detectors, plot the values for the full-energy peak efficiency versus 7-ray
energy. The plot will allow the determination of efficiencies at energies for which
standards are not available, and will show that the algorithms used in computerized
systems are providing valid efficiency calibrations.
Once the efficiencies have been determined. It is unnecessary to recalculate them
unless there is a change in resolution, geometry, or system configuration.
SAMPLE MEASUREMENTS
After the spectrometer system has been set up, the energy and efficiency
calibrations are performed, then the unknown sample can be measured.
Following the general concepts of quantitative analytical chemistry, transfer the
sample to the specimen container ana position it in the same manner as was done
during system calibration.
Measure the sample for a period of time long enough to acquire a 7-ray spectrum
which will meet the minimum acceptable counting uncertainty.
PEAK AREA CALCULATION'S
Spectral data obtained with a Ge detector are only corrected for background when
these peaks may alter the final results. In many experiments, the background may not
affect the results but is still monitored to ensure the integrity of the system.
The underlying aim of this procedure is to subtract the continuum or baseline from
the spectral data where it underlies a photopeak of interest. For operator-directed
calculations, the choice of the baseline level may be straightforward. Tne simplest way,
using a plot of the spectral data, is to draw a straight line, using judgement and
Environ-e-'-a! Measurements Laboratory
U.S Deper.-ne.Vi 0! Energy
4.5-23
-------
experience, that best describes the baseline. Then the bnselinc data can be read
directly from ihc plot and subtracted.
Pholopealts lying on a sloping baseline or one with curvature will be analyzed.
Independent of method, with Increased uncertainty. Use of data from these peaks
should be limited to those cases where there Is no other alternative. Photopcaks that
overlap with each other will also Increase the uncertainty of Ihc final result.
In order to determine nuclide concentrations, the photopeak areas corrected for
background and Interferences are divided by the count time and efficiency for the
energy of the 7-ray being calculated to give 7 photons sec"1 for the peak of Interest. If.
as Is the case for some nuclides, the branching ratio Is not accurately known and a
direct calibration was made with the same nuclide, the branching ratio and efficiency
will be one number that converts cps to Bq sec"1 for the nuclide and photopeak of
interest. If not, the 7 photons sec"1 are converted to disintegrations sec"1 by dividing
the photons sec"1 by the photons per disintegration, for the nuclide ana photopeak of
interest. The results are then corrected for attenuation or decay, or both.
Canberra Industries MicroSampo Version 2.0 (a commercial software package) Is
used at EML to perform these calculations.
While the uncertainty due to counting and calibration may represent a significant
proportion of the total uncertainty in the measurement, systematic uncertainties should
be determined and included in the above calculation. Systematic uncertainties include,
but are not limited to. reproducibility of sample position, peak analyses, decay
calculations, background subtraction, pulse pile-up. cascade summing corrections, and
self-absorption corrections.
ANALYSIS OF COMPLEX MIXTURES
OF NUCLIDES WITH KAl(Tl) DETECTORS
Because of the inherent energy resolution of Nal(Tl) detectors. 7-ray peaks in
complex mixtures of nuclides may not be separated sufficiently for quantification as
outlined above. It may not even be possible to visually locate individual peaks if their
energies are similar or their intensity is too low in relation to other 7-rays present In the
spectrum. Complex mixtures of as many as 10 to 20 radionuclides can be quantified
mathematically with computer programs using linear least squares techniques.
Wnen using these techniques, care should be given to the following parameters.
NDvemco:
4.5-24
Envnonrne-iie! I.'.=as'jrsr.er,s Lsx.'Earv
-------
A. System gain and zero energy channel.
The exact gain and zero energy channel of the spectrometer must be monitored
and recorded. If the computer analysis program performs gain and/or baseline (/,ero
energy channel) corrections on sample data, then the library of standards data must be
obtained under uniform and precise calibration conditions.
B. Library standards.
The least squares analysis technique is a linear combination of all of the data
contained in the standards library. Therefore, the standards library must contain a
spectra of every component in the sample; in addition, these spectra must be obtained
from the purest radionuclides available.
C. Counting of library standards.
All 7-ray spectra will contain a background component. The activity of the library
standards must be high enough so that this background component will be
insignificant, even though all computer programs make some kind of a background
correction.
Tne duration of the counting period for the standard library spectra should be long
enough to obtain statistically valid data, but it should be short enough so that analyzer
gain and baseline drifts are insignificant.
The activity of the library standards should be chosen so that the counting rates of
the predominant photopeaks are all about the same.
Avery Important data evaluation technique to be used with a least squares
program is a superimposed plot of the original sample data ana the computed spectral
data. A plot of residuals (the difference between the original and computed spectra) is
also very important. Tne residuals plot is very sensitive to errors that are caused by
omitting radionuclides present in the sample from the library standards.
SAMPLE MEASUREMENTS
After the spectrometer system has been set up, the energy calibrations performed,
and individual pulse-height spectra for nuclides expected to be present in samples are
obtained, then the unknown specimens can be measured and quantified.
Following the general concepts of quantitative analytical chemistry, transfer the
sample to the specimen container and position It in the same manner as was done
during system calibration. Measure the sample for a period of time long enough to
En/iro-imeVi! Usssur&merrts Labora'.o;)'
U.S Deparme.r, 0! Erieiyy
4.5-25
-------
acquire a 7-ray spectrum which will meet the minimum acceptable counting
uncertainty.
COMPUTER CALCULATIONS
WLSQ is an EML least squares Fortran computer program that can be run on a
VAX or IBM-compatible PC to resolve complex 7 spectra.
Systematic uncertainties Include, but are not limited to: reproducibility of sample
position, peak analyses, decay calculations, background substraction, pulse pile up.
cascade summing operations, and self-absorption corrections.
The uncertainty obtained from the least squares analysis can be substituted for
the uncertainty in counting and should be included to obtain an overall uncertainty of
the analysis. The uncertainties obtained from the least squares analysis are the square
roots of the diagonal elements of the inverse matrix used to solve the linear set of
simultaneous equations representing the sample spectra.
QUALITY CONTROL
The following quality control procedures are required so that the 7-ray
spectrometers maintain their energy calibrations. In addition, the systems are to be
monitored so that degradation in performance will be noticed as soon as possible.
A. Daily calibration checks.
The energy calibration of each Ge 7-ray detector is determined dally with a mixed
nuclide source consisting of and ®^Co.
In order to maintain an energy calibration of 0.5 keV/channel, count the Am-Co
source to obtain well-defined peaks. Tne 59.5 keV 7-ray line from should fall in
channel 119. The 1332.5 keV 7-ray line from ®^Co should fall in channel 2665.
If the 1Am and ®^Co peaks do not fall in the correct channels, first adjust the
DC offset of the amplifier so that the 59.5 keV 7-ray line falls in channel 119. Then
adjust the fine gain of the amplifier so that the 1332.5 keV 7-ray line falls in channel
2665.
Recount the Co-Am calibration standard to verify the peak positions and readjust
the amplifier if necessary.
November 1930
4.5-26
Environment! Measurement Uborztsry
-------
The energy calibration of each Kal(Tl) 7-ray detector is determined daily with a
nuclide source consisting of 207Bi.
In order to maintain an energy calibration of 10 keV/channel. count the 2^7Bi
source to obtain well-defined peaks. The 570 keV 7-ray line should fall in channel 57.
The 1064 keV 7-ray line should fall In channel 106.
If the 207]3i peaks do not fall in the correct channels, first adjust the DC offset of
the amplifier so that the 570 keV 7-ray line falls in channel 57. Then adjust the fine
gain of the amplifier so that the 1064 keV 7-ray line falls in channel 106.
Recount the 2®7B1 calibration standard to verify' the peak positions and readjust
the amplifier if necessary.
B. Weekly efficiency calibration and resolution checks.
Each week the same ^7Cs calibration standard is counted, recorded, analysed,
and the date is entered into a permanent data base for each 7-rav spectrometry system.
Count the ^7Cs calibration standard in the same manner as unknown samples.
Record the data for permanent storage and perform the usual data reduction analysis.
Enter the results of the analysis (Bq) and the resolution of the i;^7Cs peak (full
width at half maximum in keV] in the 7-quallty control data base.
Report any deviation from the expected values before samples are anal^ed. If
remedial action is necessary', the cause and solution of the problem must be recorded in
the laboratory logbook. A complete recalibration must be performed If any remedial
actions have been taken.
Enviro-imer,u.l kWasuremenis Laboratory
U S. Depsrmer.1 o! Energy
4.5-27
-------
ALPHA SPECTROMETRY
QUALITY ASSURANCE AND QUALITY CONTROL
Introduction
The following information pertains to the QA/QC for the Oxford
Instruments Oasis alpha-spectrometry detectors. There are currently two
units, each containing eight pressure-controlled vacuum chambers using
thin-window, ion-implanted silicon detectors. Oxford's Oasis software
package (v 3.51) is used in the operation of these instruments.
Supplies
Each chamber has its own QC alpha source and background disc. The
alpha sources are labeled by box and chamber number (i.e., 1:1,1:2, 2:1, 2:2, etc.)
and are located in labeled plastic containers on top of each instrument. The
alpha sources were electroplated onto 24-mm stainless steel discs, and the
background sources are 1.25-inch stainless steel planchets. Each alpha source
contains the following nuclides.
Nuclide
Enerery
MeV
Nominal
Activity
(dpm)
Reference Date
¦""U
4.18
100
Feb., 1995
4.77
100
Feb., 1995
2j,Pu
5.15
100
Feb., 1995
2i]A m
5.49
100
Feb., 1995
otal Activity (3-8 MeV)
400
Feb., 1995
The activities and reference dates given in the table above are nominal. The
exact activities and dates are provided in the certificates for each of the
standard sources. An example ofone of these certificates is provided with this
document.
Procedure
1. Place disc (background or alpha source) in the appropriate chamber. Do
not apply the vacuum yet.
2. On the computer, open the Sample Manager screen from the Main Screen.
3. a) Click the mouse near "Sample ID:"
b) Select appropriate ID (OX 1:1 Background, or OX 1:1 QC Efficiency)
c) Click the mouse on Re-Queue for Count.
4. Repeat step o for each chamber, then go to the Sample Scheduling screen.
-------
5. In the bottom left corner, all samples Re-Queued should be listed.
6. Click and drag each sample to its appropriate position on the instrument
diagram in the upper left corner (the squares turn blue). The orientation
of the squares is the same as in the actual instrument.
7. Apply the vacuum to each chamber.
8. Once the pressure has been stabilized in the instruments, press the button
marked "TAG" for each chamber. All the squares in the Sample
Scheduling screen display will turn yellow. Click on Refresh to ensure
that all have changed.
9. The alpha sources count for four hours, and the background sources will
count for a minimum of 16 hours and up to three days.
10. When the sources have finished, the icon next to the chamber in the Main
screen should be purple. Press "TAG" again for each chamber. The icon
should turn green. There is no need to vent the chambers. This is done
automatically at the end of the procedure.
11. Open the Sample Reviewer and make sure the Reviewer is in the
foreground.
12. a) Click the mouse near "Sample ID:", and select a chamber source.
b) Review peaks for ROI fit and energy calibration.
c) Click the mouse on Analyze.
13. Repeat step 12 for the remaining chambers.
14. When all sources have been reviewed, click the Results tab.
15. In the case of the alpha sources, print each chamber report, selecting the
source as in step 12a. Return to the Main screen.
16. In the case of the background sources, return to the Main screen, and open
the MCA screen. Select each chamber and print the ROI list. Return to the
Main screen.
17. For both alpha and background sources preset times were entered in the
system. These need to be cleared for normal counting operations. The
easiest way to do this is to completely exit the program, and then start the
program again.
-------
QUALITY CONTROL PROCEDURES FOR THE LSC
I. Purpose
This procedure provides instructions for evaluating the performance of the liquid scintillation
counter (Wallac 1414).
II. Background
The Wallac 1414 has a predefined counting protocol (Easy GLP protocol) which is used for the
quality control maintenance of the instrument. There are three unquenched sealed standards:
a background standard, a standard, and a standard. In order to evaluate the
instrument performance, the background count rate, counting efficiency and the stability of
the energy scale are data collected by this counting protocol. Maximum and minimum test
values are set to define acceptable ranges for the parameters being monitored.
In order to monitor the stability of the instrument performance adequately, the Easy GLP
protocol should be performed once every two weeks. The instrument performance report will
list a summary of the measured values from the latest count and any parameters which fall
out of range. The reports should be stored in the LSC QC notebook. If a parameter does fall
out of range the standards should be counted again. If the parameter falls within range for
the 2nd count, the instrument is fully operational. If the parameter falls out of range for 2
consecutive counts, investigations should be made to ascertain the cause of the outlier. The
instrument is not fully operational until the instrument is able to. pass the QC tests.
III. Procedure
Protocol settings
1. Click on the Easy GLP icon in the Wallac LSC program to view the protocol.
2. Click on the Edit button to edit the protocol.
3. In the Editor 1 screen, set the count time at 600 seconds (10 minutes). Set the 2 sigma error
% of counts (precision) at 2.
4. Enter the correct reference date and activity of both standards using the information on the
top of the standard vials.
5. The window settings for the standard isotopes should be set at:
3H 5-350
14C 5-650
6. Click on the Next button to go to the Editor 2 screen.
7. To define a proper minimum and maximum range for background, first measure the local
background count rate using a count time of at least 10 minutes (600 seconds).
-------
8. Determine the 3 a value of the background count by using the following formula:
3 a = 3 * SQRT(background count rate/count time)
9. Set the minimum and maximum test values for the background range at - 3 a and + 3 a,
respectively, of the local background value determined in step 7.
10. Set the minimum and maximum test values for the efficiency at - 3% and + 1%,
respectively, of the initial efficiency measured.
11. Set the minimum and maximum test values for the efficiency at - 2% and + 1%,
respectively, of the initial efficiency measured.
12. Set the minimum and maximum test values for the SQP(I) of both isotopes at - 5 and + 3
of the initial SQP(I) of both isotopes.
13. Set the minimum and maximum test values based on the Protocol settings portion of this
procedure. Enable all of the "trend plot options".
14. Enable the "plot exceptions only" option and the "only current value" option for exception
tests.
15. Define a positive and negative acknowledgement message in the appropriate box.
16. Click OK when finished editing.
Counting the standards
1. Place the background standard in the 1st position, the standard in the 2nd position,
and the l^C standard in the 3rd position of the sample rack. Place an empty rack behind it
to stop the protocol after the standards have finished counting.
2. Click on the Easy GLP icon in the Wallac LSC program to view the protocol.
3. Click on the Start button to start the count of the standards
-------
Coaxial Intrinsic Germanium Detector
IG Specifications
Manufacturer:
Model No.:
Cryostat Configuration:
Serial No.:
Bias Volt.:
Cryogenic Information
Dewar Model:
Dewar Capacity:
Static Holding Time:
Detector Cool-Down Time:
EG&G ORTEC
GMX-15190
CFG-SV-GMX / D WR-30
25-N-56QB
Negative, 3000 v
DWR-30
30 L
18 days
6 hours
Dimensions
Crystal Diameter:
Crystal Length:
Endcap to crystal:
Absorbing Layer:
Description
49.3 mm
45.1 mm
3 mm
0.5 mm (beryllium)
EG&G ORTEC model GMX photon detectors use n-Type high purity
germanium (HPGe) semi-conductor material. The n-Type Ge detector permits the
entire outer contact to be ion-implanted.
GMX Series
n-Type
HPGe Coaxial Detector
Thick Contact: 500-1000 microns
Thin Contact: < 0.3 microns ion implantation
The geometry is a coaxial configuration with a closed outer contact end which
blends into the outside cylinder surface. The advantage of using a coaxial detector
geometry is the large detector volume which is more efficient at high energy gamma
ray detection, especially for those 7-rays with small absorption cross-sections. A
deep centered contact enclosed in the closed-end configuration increases charge
collection and maintains good energy resolution. The detector element window
thickness is 0.3 microns and verv fragile. The detector has a useful energy range of 3
-------
Performance Specifications
Co-60 source
Warranted
Measured
Resolution (FWHM) at 1330 keV
1.90 keV
1.87 keV
Peak-to-Compton Ratio
44
45.4
Relative Efficiency at
15.0%
16.6%
1330 keV
Peak Shape (FWTM/FYVHM)
1.95
1.86
Peak Shape (FWFM/FWHM)
2.80
2.69
Noise Line Width (FWHM)
761 eV
QC for Coaxial Detector
Supplies
The following sources are required for QC tracking of the coaxial detector and can
be found in the standards drawer in the counting room:
Source Name Type of Source Date Sealed Ref. Date
1. EPA Pitchblende* sealed A1 can March 27,1995 May 18,1978
2. Background empty can N/A N/A
*The QC standard aluminum can was made by evenly distributing 4.986 g of EPA
Pitchblende over the can bottom. This aliquot of uranium ore was sealed in
position with epoxy to maintain a constant geometry before permanently sealing
the can.
Procedure:
The coaxial detector operates through the MCA Series 95 in user £3.
Parameters monitored on the coaxial detector are efficiency count rate, resolution,
and background for 3 peak energies: (1) 210Pb at 46.5 keV; (2) 214Bi at 609 keV; and
(3) 21-4Bi at 1764.1 keV. Efficiency and resolution counts must be performed weekly
using the EPA pitchblende can. A count time of at least 45 to 50 minutes is required
which results in approximately 6000 counts in the 210Pb region. The count rate
(cpm) of the standard at each peak of interest is used as a proxy the detector
efficiency. The full width-half maximum (FWHM) is the resolution tracking
parameter. A background count must be performed monthly (ever)' other payday)
and the count rates (cpm) for the peaks of interest should be logged. This
background count may also be used for lab analyses. Set all background ROI's
before printing the spectrum data. Log sheets found in the Ge Detector QC
-------
should also be recorded. Be sure to record the date and an)' maintenance performed
on the detector for future reference.
The QC data should be added to a running spreadsheet in the Gateway P-90
found through C:\msoffice\excel\qc\coaxial.xls. This spreadsheet calculates the
mean (±la & ±2o) for weekly efficiency and resolution data. Time-series plots of
this data should be updated quarterly and a hard copy placed in the Ge Detector QC
Notebook. The background QC spreadsheet is nested in the coaxial.xls excel file
listed above and background cpm for all peak energies should be recorded for time-
series analysis. Background count rates should be calculated and a hard copy
placed in the counting room Ge detector background folder for common usage.
This folder is located in the top filing cabinet drawer next to the coaxial detector. If
the detector exhibits unusual behavior, such as low energy (Compton) noise or peak
-------
BIOGRAPHICAL DATA SHEET
Name: William C. Burnett
Position: Professor
Telephone#: (904) 644-6703
Fax# (904) 644-2581
Soc. Sec.#: 146-36-8702
Professional address:
Department of Oceanography
Florida State University
Tallahassee, Florida 32306
email: wburnett@mailer.fsu.edu
Education:
r.ollepe or University
Major Field
Dates Attended
Degree
University of Hawaii
University of Hawaii
Upsala College
Geochemistry/Radiochemistry
Geochemistry
Geology
1971-1974
1968-1971
1964-1968
Ph.D.
M.S.
B.S.
PROFESSIONAL EXPERIENCE:
(A) Positions:
Dale?
Organization
Position
1987-present Department of Oceanography, Florida State Univ
1981-1987 Department of Oceanography, Florida State Univ
1977-1981 Department of Oceanography, Florida State Univ
1976-1977 Inst. Nuclear Geophysics, Federal Univ. Brazil
1974-1976 Dept. Earth/Space Sci., SUNY, Stony Brook
Professor (Chair '91-'94)
Associate Professor
Assistant Professor
Visiting Scientist
Postdoctoral Fellow
(B) Pertinent Research, Teaching and/or Related Activities
•Director, Environmental Radioactivity Measurement Facility, Department of Oceanography,
Florida State University; 1990-present.
•Guest Instructor, Training Department, Canberra Industries, lnc.\ courses instructed: Basic
Alpha Spectrometry, Advanced Alpha Spectrometry; 1989-present.
•Technical Advisor for Radiochemistry, Environmental Physics, Inc., General Engineering
Laboratories, Charleston, S.C.; 1991-present.
•New Zealand National Research Advisory Council (NRAC) Senior Fellowship - Institute of
Nuclear Sciences, Wellington, New Zealand (Jan. - May, 1984)
• Over 25 grants received (approx. S4 million) from the NSF, DOE, EPA, NOAA, DOD,
American Chemical Society, Florida State Agencies, and elsewhere. Most funded research
projects concerned measurement of radioisotopes in the environment.
(C) Supervision of 8 Theses and 4 Dissertations. Membership on 12 Graduate Student Committees
(D) Selected Publications (Of -90 peer-reviewed papers):
Cable, J.E., W.C. Burnett, J.P. Chanton, and G. Weatherly, 1996. Modeling groundwater flow
into the ocean based on 222Rn. Earth Planet. Sci. Lett.. 144, 591-604.
Burnett, W.C., J.E. Cable, D.R. Corbett, and J. Chanton, 1996. Tracing groundwater flow into
surface waters using natural 222Rn. In: Proceedings, "The International Symposium on
Groundwater Discharges to the Coastal Zone" (ed. R. Buddemeier), Russian Academy of
Sciences, Land-Ocean Interactions in the Coastal Zone (LOICZ), July 6-10, 1996, Moscow.
Corbett, D.R., W.C. Burnett, P.H. Cable, and S.B. Clark, 1998. A multiple approach to the
determination of radon fluxes from sediments. Jour. Radioanalvtical & Nuclear Chemistry, in
press.
Burnett, W.C., P.H. Cable, and J. P. Chanton, 1995. A simple passive collector for direct
measurement of radon flux from soil. Jour. Radioanalvtical Nuclear Chem.. 193, 281-290.
Burnett, W.C.. P.H. Cable, and R. Moser, 1995. Determination of radium-228 in natural waters
-------
RESUME
ALAN E. BAKER
Northwest Florida Water Management District 1820 May fair Rd.
Bureau of Resource Regulation Tallahassee, FL 32303
Box 3100 Havana, FL 32333-9700 (850) 386-6706
Office: (850) 539-5999; FAX: (850) 539-4380
email: allen.baker@nwfwmd.state.fi.us
abaker@ocean.fsu.edu
Personal Data
Born 28 March 1971, Hartford, Connecticut. Married.
Education
B.S., Geology, Florida State University, 1994
Experience
1997 - Present: Hydrogelogist, Northwest Florida Water
Management District (NWFWMD). Midway, Florida.
Bureau of Resource Regulation
Responsible for the evaluation and management of geologic and hydrogeologic
information; ground and surface water withdrawal information; computer modeling
data; well construction; and other information to assist the bureau with the technical
review of consumptive use permit applications. Additional responsibilities include
the monitoring and evaluation of data submitted and actions taken by consumptive
use permittees to determine compliance. Drafting of staff reports, compilation of
water use projections and resource impact evaluations while summarizing
consumptive use requests. Experience with Global Positioning Systems and the
Florida Unique Id well tagging program. Deal frequently with the public
concerning regulator}' matters.
1994 - Present: Research Assistant, Environmental Radioactivity
Measurement Facility (ERMF), Department of
Oceanography, Florida State University
Responsibilities in the EMRF include sampling monitor wells and
fieldpreparation of gases and liquids from monitor wells for chemical and
radio-chemical analyses. Analysis of chemical components and light stable
radioisotopes. Calibration and maintenance of radiation detection
instrumentation, radioisotopic separation by ion chromatographic techniques,
and reduction of radiochemical data including 222]^ jn gases and liquids and
226Ra< 238u5 235u5 234jj7 210pt)j 210po jn liquids and solids
using alpha, beta, and gamma spectrometric techniques. In addition prepares
and measures sediment core samples for 21 Opt) analyses to determine
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1995-1996 Research Associate, Nanomolar Geochemistry Group,
Department of Oceanography, Florida State University
Responsibilities in the Nanomolar Geochemistry Group include ultracleaning
of sampling containers, preparation of field instrumentation and sampling
equipment, and assisting in preparatory work for chemical analyses by
atomic adsorption spectrometry.
References
Dr. William Burnett, Professor.
Environmental Radioactivity Measurement Facility
Department of Oceanography
The Florida State University
Tallahassee, FL 32306-3048
Office: (850) 644-6703
FAX: (850) 644-2581
email: burnett@ocean.fsu.edu
Dr. William Landing, Associate Professor
Department of Oceanography
The Florida State University
Tallahassee, FL 32306-3048
Office: (850) 644-6037
FAX: (850) 644-2581
email: landing@ocean.fsu.edu
Michael Schultz
National Institute of Standards & Tracers
245/C114
Gaithersburg, MD 20899
Office: (301) 975-4336
Fax: (301)-926-74l6
email: michael.schultz@nist.gov
Publications
(r)
Hull, C. D., Baker, A. E., Duffy, J., and Burnett, W. C. submitted, Comparison of PERALS
and alpha spectrometric measurements of U isotopes and total U in solutions: Abstract, 42n(^
Annual Conference on Bioassay, Analytical and Environmental Radiochemistry, Oct. 13-17,
1996, San Francisco, CA.
Hobbies
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310 Nassau Drive
Baton Rouge, Louisiana 70815
PETER HANS CABLE
(504) 272-1423 (H)
(504) 862-3166 (W)
EMPLOYMENT HISTORY
1998 to present: Laboratory Manager, Department of Geology, Tulane University, Dr. Brent McKee
•Manage laboratory activity including instrument calibrations, tracer preparation, and equipment
maintenance.
•Prepare for and participate in fieldwork.
•Assist students with a variety of geochemical and oceanographic research projects.
November, 1996 to December, 1997: Project Scientist, Environmental Science and Engineering,
Gainesville, Florida; Ying Dong Pan
•Manage sample flow through the actinide chemistry group.
•Supervise laboratory technicians in the actinide chemistry group.
•Upgrade and improve current chemical methods and develop new methods to meet client needs.
•Analysis of client samples.
1990 to November, 1996: Laboratory Manager, Environmental Radioactivity Measurement
Facility, Department of Oceanography, Florida State University; Dr. W.C. Burnett
•Develop novel radiochemical separations for uranium-series and transuranic element analysis.
•Manage laboratory activity including instrument calibrations, tracer preparation, and ordering
supplies.
•Prepare for and participate in fieldwork.
•Assist students with a variety of geochemical and oceanographic research projects.
1988 to 1990: Laboratory Technician, Department of Oceanography, Florida State University; Dr. W.C.
Burnett
•Assisted with sample preparation and fieldwork.
1987 to 1988: Laboratory Technician, Department of Chemistry, Florida State University; Dr. L.
Mandelkem
•Studied the effects of differing crystallinities on the physical properties of polymers.
1988: Recitation Instructor, Chemistry for Liberal Studies (CHM 1020), Department of Chemistry, Florida
State University; Dr. Gregory Choppin
•Answered questions and solved example problems for students in introductory chemistry.
PROFESSIONAL EXPERIENCE
October 28 to November 8, 1996: Co-organizer and Lecturer, International Atomic Energy Agency
Technical Cooperation Program "The Assessment of Alpha Emitting Radionuclides in Marine
Samples", Cekmece Nuclear Research and Training Centre, Istanbul, Turkey
•Organized laboratory exercises for 25 workshop participants from the Black Sea region
(Romania, Bulgaria, Ukraine, and Turkey).
•Presented lectures on environmental sample analysis including natural and artificial radioactive
elements.
•Demonstrated and supervised laboratory experiments.
1989 to present: Consulting Faculty, Canberra Industries Inc., Meriden, CT; Rob Woodard
•Teach laboratory portion of beginning and advanced alpha spectrometry training courses.
•Topics include sample pretreatment and digestion, ion-exchange and extraction chromatographic
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PROFESSIONAL EXPERIENCE CONTINUED
1990 to present: Technical Consultant, Environmental Physics Inc., Charleston, S. C. and Eichrom
Industries, Darien, IL.
•Development of radiochemical methods.
FIELD EXPERIENCE
1988 to 1996: Florida, U. S. A.
•Made numerous trips to north and central Florida to collect groundwater and phosphogypsum samples
for radiochemical analysis.
•Measured 222Rn soil gas concentrations and atmospheric fluxes.
1994 to 1996: Wakulla Springs, Florida
•Worked on the design and calibration of a new instrument to determine integrated radon concentrations
in water.
1992 to 1994: R/V Seminole , Gulf of Mexico
•Studied benthic fluxes on the Florida Platform.
•Took numerous offshore cruises to measure groundwater seepage and take CTD profiles.
•Collected sediment and seawater samples for iracer analysis
June, 1993: Palau, Micronesia
•Investigations into the formation of insular phosphate deposits.
•Collected and analyzed water and sediment samples from marine lakes.
•Determined sediment accumulation rates using excess 210pb dating techniques.
April to May, 1990: Institute of Nuclear Science, Lower Hutt, New Zealand
•Determination of the residence time of the waters in the Wairakei hydrothermal system.
•Assisted in sample collection and analysis of geothermal waters.
EDUCATION
1986 to 1987: Chemistry major at Florida State University, Tallahassee, Florida
1985: Associate of Arts Degree, Tallahassee Community College, Tallahassee, Florida
PUBLICATIONS
Cable, J.E., W.C. Burnett, J.P. Chanton, D.R. Corbett. and P.H. Cable. 1997. Field Evaluation of
seepage meters in the coastal marine environment, Esiuarine, Coastal and Shelf Science 45: 367-375.
Bugna, G.C., J.P. Chanton, J.E. Cable, W.C. Burnett, and P.H. Cable. 1996. The importance of
groundwater discharge to the methane budgets of nearshore and continental shelf waters of the
northeastern Gulf of Mexico, Geochimica et Cosmochimica Acta 60(23): 4735-4746.
Koskelo, M.J., W.C. Burnett, and P.H. Cable. 1996. An advanced analysis program for alpha-particle
spectrometry, Radiochemistiy and Radioactivity 1 {\)\ 18-27.
Burnett, W.C. and P.H. Cable. 1995. Radium-228 in natural waters via extraction chromatography,
Radiochemistry and Radioactivity 6(2): 36-44.
Burnett, W.C., P.H. Cable, and J.P. Chanton. 1995. A simple device for direct measurement of radon
flux from soil, Journal of Radioanalytical and Nuclear Chemistry 193(2): 281-290.
Marcus, N.H., R.V. Lutz, W.C. Burnett, and P.H. Cable. 1994. Age, viability, and vertical distribution
of zooplankton resting eggs from an anoxic basin: Evidence of an egs bank, Limnology and
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TECHNICAL REPORTS AND MEETING PROCEEDINGS
Burnett, W.C., J.B. Cowart, P. LaRock, C.D. Hull, Z. Zhang, J. Chcrrier, P.H. Cable, and G. Schaefer.
1995. Microbiology and radiochemistry of phosphogypsum, Florida Institute of Phosphate Research
Final Report, Publication No. 05-035-115.
Burnett, W., J. Chanton, G. Weatherly, J.E. Young, G. Bugna, R. Corbett, and P.H. Cable. 1994.
Freshwater Input to the Gulf of Mexico via Springs and Seeps, p. 67-73. In Northeastern Gulf of
Mexico Physical Oceanography Workshop Proceedings, (ed) A. Clarke, Florida State University,
Tallahassee, Florida.
Burnett, W.C., J.B. Cowart, W. Tai, and P.H. Cable. 1991. Investigations of radon and radon daughters
in surficial aquifers of Florida, Florida Institute of Phosphate Research Final Report, Publication No.
05-032-093.
MANUSCRIPTS IN REVIEW OR IN PREPARATION
Corbett, D.R., W.C. Burnett, P.H. Cable, and S.B. Clark. Radon tracing of groundwater input into Par
Pond, Savannah River Site, in press, Journal of Hydrology.
Brenner, M., T.J. Whitmore, M.A. Lasi, J.E. Cable, and P.H. Cable. Influence of Aquatic Macrophytes
on Water-Colurrm Nutrient Concentrations: a Paleolimnological Perspective, in review, Journal of
Paleolimnology.
Corbett, D.R., W.C. Burnett, P.H. Cable, and S.B. Clark. A multiple approach to the determination of
radon fluxes from sediments, in review, Journal of Radioanalytical and Nuclear Chemistry.
Cable, P.H. and W.C. Bumett. Analysis of Promethium-147 in aqueous samples, in prep., for submission
to Journal of Radioanalytical and Nuclear Chemistiy.
Cable, P.H. and W.C. Burnett. Investigating the Chemical and Physical Controls on Electrodeposition for
Alpha Spectrometry, in prep., for submission to Radiochemistiy and Radioactivity.
ABSTRACTS AND PRESENTATIONS
Cable. P.H. and W.C. Burnett. 1997. Analysis of Promethium-147 in aqueous samples. 43^ Annual
Conference on Bioassay, Analytical, and Environmental Radiochemistry, Charleston, S.C., November
09-13, 1997.
Cable. P.H.. W.C. Burnett, D. Hunley, J. Winne, W. McCabe and R. Ditchburn. 1994. Investigating the
chemical and physical controls on electrodeposition for alpha spectrometry, 40^ Annual Conference on
Bioassay, Analytical, and Environmental Radiochemistry, Cincinnati, OH, November 14-18, 1994.
Schultz. M.K.. P.H. Cable, W.C. Burnett, J. Westmoreland, and H. Coleman. 1994. Distribution of
uranium and transuranic elements in soils and sediments, 40^ Annual Conference on Bioassay,
Analytical, and Environmental Radiochemistry, Cincinnati, OH, November 14-18, 1994.
Corbett, D.R., W.C. Burnett, P.H. Cable, and S.B. Clark. 1994. Determination of the 222Rn budget in
Par Pond, Savannah River Site, 40ik Annual Conference on Bioassay, Analytical, and Environmental
Radiochemistry, Cincinnati, OH, November 14-18, 1994.
"ieh, C.C., P.H. Cable, and W.C. Burnett. 1994. Separation of 2-51Pa from environmental samples, 40&
Annual Conference on Bioassay, .Analytical, and Environmental Radiochemistry, Cincinnati. OH,
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ABSTRACTS AND PRESENTATIONS CONTINUED
Burnett. W.C.. C.D. Hull, P.H. Cable, J. Cherrier. 1993. Radionuclides in Phosphogypsum: Migration
and bacterial control, International Conference on the Chemistry and Migration Behavior of Actinides
and Fission Products in the Geosphere, Charleston, S. C., December 12-17, 1993.
Cable. P.H.. W.C. Burnett, and J.P. Chanton. 1993. A simple device for measurement of radon flux from
soils, 39^ Annual Conference on Bioassay, Analytical, and Environmental Radiochemistry, Colorado
Springs, CO, October 11-15, 1993.
Burnett. W.C.. C.D. Hull, and P.H. Cable. 1993. Radium and other radionuclides in phosphogypsum,
39ik Annual Conference on Bioassay, Analytical, and Environmental Radiochemistry, Colorado
Springs, CO, October 11-15, 1993.
Burnett, W.C., C.D. Hull, J.E. Young, and P.H. Cable. 1993. A simple self-absorption correction for
gamma-ray counting of soils and sediments, 39& Annual Conference on Bioassay, Analytical, and
Environmental Radiochemistry, Colorado Springs, CO, October 11-15, 1993.
Chanton. J.P.. W.C. Burnett, J.E. Young, P.H. Cable, G. Bugna, D.R. Corbett, and G. Weatherly.
1993. 222Rn and CH4 tracing of groundwater discharge into the ocean. EOS, vol. 74, no. 16, p. 148.
American Geophysical Union, Spring meeting, Baltimore, MD, May 24-28, 1993.
Youne. J.E.. W.C. Burnett, G. Bugna, P.H. Cable, J.P. Chanton, D.R. Corbett, and G. Weatherly.
1993. Tracing groundwater discharge into the ocean, The Oceanography Society, Seattle, WA, April 13-
16, 1993.
Corbett. D.R.. W.C. Bumett, J.P. Chanton, P.H. Cable, and J.E. Young. 1993. Groundwater seepage in
the Gulf of Mexico, The Geological Society of America (Southeastern Section), Tallahassee, FL, April
1-2, 1993.
Cable. P.H. and W.C. Burnett. 1992. Radium-228 in natural waters via extraction chromatography, 38^
Annual Conference on Bioassay, Analytical, and Environmental Radiochemistry, Santa Fe, NM,
November 1-6, 1992.
Cable. P.H. and W.C. Burnett. 1989. Measurement of radon concentrations and emanation rates via
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Roger Wong
2850 McArthur Street
Tallahassee, FL 32310
W (850) 644-6525
H (850) 574-3607
email: rwong@ocean.fsu.edu
Education:
Sept. 1985- Georgia Institute of Technology, B.S. in Health Physics (September 1989)
Sept. 1989 Course work - Nuclear chemistry, radiation biology, radiation protection and safety
radiation shielding, health physics instrumentation, statistics, calculus, physics.
Jan. 1996- Florida State University, projected M.S. in Chemical Oceanography (May 1998)
present Research thesis - Develop an improved assay for measuring gross alpha/beta
concentrations in soil and sediments. Course work - Environmental radiochemistry,
nuclear chemistry, geochemical tracers in the ocean, marine isotopic chemistry, marine
geology, biogeochemistry, atmospheric chemistry, chemical oceanography.
Work Experience:
Jan. 1990- General Engineering Laboratories, Position: Laboratory Technician
Mar. 1991 Responsibilities: Prepare environmental samples for gross alpha/beta, tritium and
total radium analyses. Operate and maintain the liquid scintillation counter and gas-
flow proportional counter. Perform data reduction, data review and QC maintenance
of instrumentation. Develop procedures and train technicians to operate count room
instrumentation.
Oct. 1991- Westinghouse Savannah River Company, Position: Scientist
Aug. 1994 Responsibilities: Calibrate and maintain liquid scintillation counters, alpha
spectroscopy instrumentation and gas-flow proportional counters, review data for
quality control/assurance, analyze/interpret environmental radiological data and
write technical reports, train technicians to operate count room instrumentation.
Oct. 1994- North Carolina Division of Radiation Protection, Position: Environmental scientist
Dec. 1995 Responsibilities: Technical review of the radiological environmental monitoring
aspects of the license application for a low-level radioactive waste disposal facility,
developed an organized review system for a team of state technical personnel involved
in the review process, developed a special study and collected samples for analyzing
spatial and temporal variations of tritium in surface water in a cooling lake utilized by
a nuclear power plant.
Summer Performed thesis research at the Savannah River Ecology Laboratory for developing an
96 and 97 improved assay for measuring gross alpha/beta radioactivity in soil.
Achievements:
Publications - Journal of Radioanalytical and Nuclear Chemistry, in press, "Direct
Counting of Soil Wafers - An Improved Total Alpha/Beta Screening Analysis"; a paper
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Presentations - 42nd Annual Conference on Bioassay, Analytical, and Environmental
Radiochemistry, 1996, "Development of an improved assay for determining gross
alpha/beta concentrations in soil and sediments - Direct counting of soil wafers";
43rd Annual Conference on Bioassay, Analytical, and Environmental Radiochemistry,
1997, "Development of an improved assay for determining gross alpha/beta
concentrations in soil and sediments - Liquid scintillation counting."
Field work - Participated in 2 field cruises with the FSU Geology department for
collecting sediment samples off the Gulf Coast. Dissolved oxygen, salinity, and
temperature measurements were made at depth and sediment was analyzed for
microbial activity.
Teacher assistant for undergraduate oceanography courses during Spring 98.
Member of the SRS Chapter of the HP Society 1991-1994.
Skills:
Computers: Experienced with using IBM PC, Apple and DEC VAXstations; Software:
Experienced with using Canberra alpha management system, Procount, Oxford Oasis
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Author: Kim Barrett
Revision Date: 6/3/97 TMF
Editor: Christa Kinyon, 5/10/1998
NU-045-1
DISTILLATION OF TOTAL CYANIDE FROM WATER AND SEDIMENT SAMPLES
SCOPE AND APPLICATION
1.1. This method details the distillation of total cyanide from water and sediment samples and is
addaptation of the sample preparation for total cyanide analysis described in EPA method 335.2.
Distilled samples produced by these means are suitable for analysis through colorimetric methods
(Lachat or Alpkem instrumentation).
2. SUMMARY OF THE METHOD
2.1. Total cyanide, as hydrogen cyanide (HCN), is released from cyanide complexes during reflux-
distillation and absorbed onto a scrubber containing sodium hydroxide. The concentration of
absorbed cyanide ions may then subsequently be determined colorimetrically.
3. APPARATUS AND EQUIPMENT
3.1. Eppendorf 1 OOuL pipette.
3.2. Oxford Pipette (Adjustable volume, l-5mL).
3.3. Mettler PE360 Top loading Balance.
3.4. Stainless Steel Spatulas.
3.5. Aluminum and polystyrene weigh boats.
3.6. Fisher Vortexer "Genie 2."
3.7. Distillation System: Midi-Vap Model MC-100
3.7.1. Digestion Block
3.7.2. 50 mL distillation tubes.
3.7.3. Reflux impingers.
3.7.4. Absorber impingers
3.7.5. Cold finger condensers.
3.8. Vacuum pump
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3.10 Boiling Beads
3.11 50 ml centrifuge tubes
4. REAGENTS AND CHEMICALS
4.1. Deionized water (D1 water).
4.2. 0.25 M Sodium Hydroxide solution: 20 g solid NaOH dissolved into 2L DI water.
4.3. 1:1 Sulfuric acid: 50% (v/v) H2SO4
4.4. 51% magnesium chloride solution: 51% MgCI and 49% DI water (w/w).
4.5. Standards and spiking solutions
4.5.1. SPEX standard reference material.
4.5.2. PQL solution: 0.02 ug/mL KCN.
4.5.3. Spiking Solution: 0.50 ug/mL KCN.
4.6 Sulfamic Acid, powder.
NOTE: Record all pertinent information (lot #, date opened/made, preparer, etc) on the digestion
sheet for all reagents.
5. SAMPLE COLLECTION, PRESERVATION, AND HANDLING
5.1. Samples for cyanide analysis are stored in the nutrients refrigerator (#4) located in the Receiving
Room.
5.2. Water samples are preserved prior to distillation with NaOH to a pH >10. Soil and sediment
samples are not preserved.
6. SAMPLE PREPARATION PROCEDURE
6.1. Sample Homogenization ( for soils and sediments).
6.1.1. If the sample cannot be thoroughly mixed within its container without spilling, empty the
entire sample into a stainless steel tray. Remove any rocks, shells, and twigs from the
samples and mix each thoroughly to achieve homogeneity, then return the sample to the
jar.
6.1.2. The method of homogenization is dependent on the type of sediment and can be
accomplished by the following methods:
• slurry sample - a separation is evident between loose, wet sand and the water
layer and is easily mixed. Mix the sample thoroughly with a stainless steel
spatula until homogeneous.
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• paste sample - organic matter is obvious in the sample. The sample has enough
moisture in it to create a paste when mixed. Remove any rocks, shells, twigs,
etc. Mix thoroughly with a stainless steel spatula.
• sand sample - loose, dry sediment/soil that needs minimal breaking up of large
particles. Mix thoroughly, breaking up any clumps of sand. A mortar and
pestle can be used.
• clay sample - dry, hard, compacted sediment that requires crushing of particles.
Mix thoroughly. A mortar and pestle can be used.
6.2. Place a dry vessel onto the balance and tare out the balance . Weigh into the vessel approx. 1
gram of homogenized sample. Record the weight to the nearest 0.00 lg on the logsheet in the field
marked "sample weight." Make sure that all of the weighed sample is on the bottom of the vessel
and that none has dropped onto the balance outside the vessel, (use some of the homogenized
sample for the percent solids determination as well). Weigh the quality control (QC) samples
such that the weights are all within ±0.005g of each other (see section 6.4 on selection of QC
samples).
6.3. Percent Solids Determination
6.3.1. Label an aluminum weigh boat with the sample number. For each sample weigh the boat
and record this value in the Percent Solids Logbook as the tare weight. Tare the balance
and place approx. 10 grams of the sample into the boat. Record this value as the sample
wet weight. Repeat for each sample recording values to the nearest 0.001 gram.
6.3.2. Place the boats with samples into a drying oven (103-105° C) overnight. Remove the
samples from the oven and allow to cool in a dessicator for approx. 15 minutes.
6.3.3. Weigh each sample and record the weight to the nearest 0.001 gram in the Percent Solids
logbook as dry weight + tare. Subtract the tare weight from this value to determine the
sample's dry weight. The percent solids of the sample can be determined by the
following calculation:
dry wt
% solids = X 100%
wet wt
The dry weight of the sample digested must be determined by the following calculation:
dry wt
dry weight of sample = X wet sample weight
wet wt
Report the dry weight of the sample on the logsheet in the field marked "sample dry
weight."
6.4. Quality Control Samples
6.4.1. Selected quality control samples are required with each sample analysis batch.**
Digestion Blank: One per digestion of <20 samples.
Sample Matrix Spikes: Two per digestion batch (must be a duplicate sample matrix).
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Duplicates: One set of duplicate samples per digestion batch. (In general use the same
sample used for matrix spikes).
A digestion batch is defined as a set of 20 samples or less of the same matrix,
group The five possible matrix groups are:
1. W-GROUND:
W-SURF-FRH:
W-DRINKING:
Ground water
Fresh surface water
Drinking water
2.
W-SURF-SLT:
Salt surface water.
3.
W-EFFLUENT:
W-INFLUENT:
W-OTHER:
Effluent
Influent
Any other water sample
4.
S-SOIL:
S-FRHWTRSD:
Soil
Fresh Water Sediment
5.
S-MARINESD:
S-OTHER:
Marine Sediment
Soil7sediment not fitting in above groups
6.4.2. All samples in the same matrix group are to be digested in the same batch. If there are
>20 samples of the same matrix, group then batches of twenty samples are digested
together. Each batch requires its own set of quality control samples.
6.4.3. Selecting Samples for Quality Control: Randomly choose a sample to be used as
duplicates and matrix spikes. This sample will be prepared with a duplicate, a matrix
spike and duplicate spike. Thus this one sample will be poured or weighed out 4 separate
times. To the weighed out sample add the appropriate amount of Spiking Solution (See
below, spike samples after they are in the block under the hood).
6.5. Load samples to be analyzed into clean Reflux tubes
6.5.1. For Aqueous Sample: Pour 50 mL of sample or an aliquot diluted to 50 mL into the
Reflux tube. Add 2 boiling beads. "
6.5.2. For Solid Sample: Weight 1.0 g. of sample [nearest 0.001 g] into the Reflux tube and
dilute to 50 mL with DI water. Add 2 boiling beads.
6.6. Place Reflux tubes containing sample into an Absorber Tube Rack.
6.7. Add 40 mL 0.25 M NaOH into a clean Absorber tube ( use one tube for each sample to be run.).
6.8. Place the Absorber tubes into the front row of holes on the distillation blocks.
6.9. Place a Reflux tube containing sample into the left most heat block hole. Continue filling the
holes proceeding to the right until all sample tubes are in the block.
6.10 Spike the necessary samples with lOOul of0.50ug/mL KCN.
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6.11 Add 0.2g Sulfamic Acid to each sample tube.
6.12. Place a Reflux Impinger with the gas exit tube facing the rear of the block into each Reflux tube.
The ground glass connections must be lubricated with a very light coat of high vacuum grease
prior to insertion.
6.13. Place an Absorber Impinger with the gas inlet tube facing the rear of the block into each Absorber
tube. The ground glass connections must be lubricated with a very light coat of high vacuum
grease prior to insertion.
6.14. Connect each Absorber Impinger gas inlet tube to the corresponding Reflux Impinger gas outlet
tube.
6.15. Connect each Absorber Impinger vacuum tube to the corresponding valve tube.
6.16. Place a Cold Finger Condenser with water ports facing to the rear into each Reflux Impinger tube.
The ground glass connections must be lubricated with a very light coat of high vacuum grease
prior to insertion.
6.17. Connect the cold finger water tubes to the water manifold QD adapters to the rear of the unit. The
lower tube connects to the forward manifold (water outlet) and the upper tube connects to the rear
manifold (water inlet).
6.18. Turn off each vacuum valve (twist each knob all the way to the right).
6.19. Check to make sure an excess gas trap is loaded with 1 M NaOH and connected to the vacuum
line connected to the block.
6.20. Turn on cooling water and adjust to 6 GPH for each sample position, i.e. for 4 samples present
adjust flow to 24 GPH.
6.21. Turn on vacuum to unit and adjust each valve to give a flow of three bubbles per second in each
Reflux tube. This roughly corresponds to the foaming in the absorber tubes reaching
approximately 1cm above the 50 mL line.
6.22. Allow vacuum draw for 5 minutes.
6.23. Inject 5 mL of 50 % (v/v) H2SO4 through the air inlet of each Reflux Impinger using an oxford
pipette.
6.24. Allow vacuum to draw for 5 minutes.
6.25. Inject 2 mL magnesium chloride solution through the air inlet of each Reflux Impinger. Inject
another 2 mL using an oxfore pipette if excessive foaming occurs.
6.26. Turn unit on (red rocker switch) and light will glow.
6.27. Turn on timer and depress push-button. Green timer light and amber heat lights will glow. The
timer allows for 15 minutes heat up time (may vary relative to location and hood conditions) and
90 minutes of refluxing time. The heat block is factory preset to 125° C.
6.28. The timer will automatically turn off heat block after time has expired. Vacuum draw and
cooling water are unaffected.
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6.29. Allow to cool 15 minutes before turning off cooling water and vacuum.
6.30. Disconnect tubing from the vacuum inlet.
6.31. If there is not enough time to rinse the frits and bring the samples to volume, then remove only the
absorber impinger tubing, rinse out the frit with 0.25 M NaOH (see 6.31 & 6.32) and parafilm the
opening. The samples can sit overnight.
6.32. Lift the absorber impinger so that the sample (in NaOH) will drain out of the frit.
6.33. With the impinger still lifted, push the remaining liquid out with air (using an empty water bottle).
Squirt 0.25 M NaOH into the impinger tube. Push out with air. Repeat 3 times. Be sure to use
small enough amounts so that the final sample volume does not go over the 50 mL line.
6.34. Place impinger in a 1000 mL beaker half filled with distilled water.
6.35. Wipe each ground glass connection with a paper towel to remove the vacuum grease.
6.36. Bring the sample volume to 50 mL with 0.25 M NaOH.
6.37. Pour sample into labeled tubes. Label tubes with sample l.D and distillation date. (Labels can be
printed via sample manager).
7. SAFETY/HAZARDOUS WASTE MANAGEMENT
7.1. Samples: All samples are handled as if they contain hazardous amounts of all analytes. Gloves
should be worn at any stage requiring contact with the sample. Excess sample should be disposed
of in the containers labeled CN Waste
7.2. Standards: Gloves should be worn when handling any of the spiking solutions. Any excess
spiking solutions should be disposed of into the containers labeled CN Waste
7.3. Reagents: Gloves should be worn when handling any reagents (NaOH, etc). Reagents should be
added to samples in a fume hood with the sash lowered as far as possible; both to reduce exposure
to fumes and protect in case of splashing.
8. REFERENCES
8.1. EPA Method 335.2. (Revision 4-79-020)
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i^%) ^yi?
Revision:04/20/98
Author: C. Kinyon, TMF
Edited by: C. Kinyon, M. Emad (5/10/1998)
MT-024-1
PREPARATION OF WATER SAMPLES FOR METALS ANALYSIS By ICP-
AES, ICP-MS and ICP-Trace
1. SCOPE AND APPLICATION
1.1. This method details the digestion of water samples for metals analysis and
is applicable to surface, ground, drinking, effluent, saline and waste
9 2
waters. This method is a modification of EPA Method 200.2.
2. SUMMARY OF THE METHOD
2.1. Water samples are heated with nitric acid and hydrochloric acid to reduce
interference by organic matter and to convert various metalic species
(organic and inorganic)to a form that can be determined by AA, ICP or
ICPMS.
3. APPARATUS AND EQUIPMENT
3.1. 50 mL graduated cylinder
3.2. 75 mL Pyrex culture tubes with Teflon caps for TCLP extract preparation
and/or 75 ml Teflon tubes for all other water sample preparation.
3.3. Plexiglass Digestion Clean Box.
3.4. Westco AD 4020 Heating Block (Placed inside the Clean Box, 3.3)
3.5. Pipettes
3.5.1. 5 0 uL Eppendorf
3.5.2. 100 uL Eppendorf
3.5.3. 200 uL Eppendorf
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3.5.5. 5-10 ml Oxford, mainly used for dilution of samples.
3.6. Fisher Vortex Genie 2
4. REAGENTS AND CHEMICALS
4.1. Trace Metal grade Nitric acid
4.2. Trace Metal Grade Hydrochloric acid
4.3. Deionized Water
4.4. Spiking and PQL Solutions
Are prepared by the Analysis group. Inform the supervisor of the Analysis
and the Inorganic Preparation Group when the prepared stocks are either
close to expiration, as inidicated by label on the bottle, or about to run out.
4.4.1. See Appendix (A) for details.
5. SAMPLE COLLECTION, PRESERVATION AND HANDLING
5.1. Water samples are preserved at the time of sampling in the field with nitric
acid to a pH of 2 or less. Sample pH is checked at the receiving room
upon arrival. Samples are stored at room temperature in the Metals
Water Samples storage room.
6. SAMPLE PREPARATION PROCEDURE
Prepare a sample backlog and select "conductivity" information as one of the
required fields of information. Samples greater than 3000 conductivity are diluted
with minimum amount of water to reach a conductivity value of just less than
3000 prior to digestion. The dilution factor information must be indicated clearly
on the preapration information sheet. Metals water samples are stored in the
Metals Water Samples storage room in the receiving area of the laboratory. The
sample custody must be transfered to the preparation staff following the proper
Logging procedure and in the presence of a Custodian to maintain the sample
Chain of Custody (COC).
6.1. Prior to digestion all glassware must be cleaned according to the SOP for
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6.2. Wipe any dust and particulates from the interior of the surface of the
heating block and the Clean Box with a paper towel dampened with DI
water. Turn on the heating block and set the temperature to a setting that
will heat the samples to 95° C. For most heating blocks, this temperature
is around 125° C.
6.3. Make an exact count of the tubes required for the digestion set, including
the QC samples (See section 7). All metal water samples except TCLP
extracts are prepared in Teflon tubes. TCLP extracts are prepared in Pyrex
glass culture tubes. Prepare the necessary labels with any spike
information, dilution factor(s) and other pertinent information on them and
apply to the tubes.
6.4. Rinse each tube 10 times with DI water, each time pouring the contents of
the tube over the cap to clean it as well.
6.5. Obtain a 50 ml graduated cylinder and clean it by rinsing the vessel with
1:1 nitric acid followed by several rinses with DI water. Tighten the
sample bottle cap and thoroughly shake the bottle and its content to ensure
a good mixing. Then, use the 50 mL graduated cylinder and transfer 50
mL of the each sample into the respectively labeled tube and cap the tube.
After each sample transferr rinse the graduated cylinder with 1:1 Nitric
and 6-7 times with DI water. When pouring up the duplicates and spikes,
shake the sample well in between each sample aliquat that is poured.
NOTE: Salt samples and samples with high conductivity are diluted
prior to digestion to reduce matrix interference. See
introduction to section 6 for details. All Superfund samples are
digested at a 1:2 dilution.
6.6. When all of the samples have been poured, use a fine point permanent
marker, such as a Sharpie, to draw a line at the base of the meniscus
indicating 50 ml volume. This is important in bringing the volume back to
50 mL after the heating step.
6.7. At this time ask another member of the staff to function as your spiking
observor. Prepare the matrix spikes according to the elements to be
analyzed. Refer to appendix (A) as a guide and pipette the appropriate
aliquots of each standard mixture into each sample to be spiked. The
observor insures that you are adding the right amount of spike to the
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NOTE: Minerals (Al, Ca, Fe, Mg, K, Na) are analyzed by ICP only.
Pour a separate aliquat for preparing a sample with a mineral
spike. Do not mix with the trace element spike.
6.8. The following operation are conducted in the hood. Make sure the fume
hood is "ON" and operating properly. If not notify the staff in charge of
safety and the superivor immediately. Remove the caps from the sample
tubes and place them face down on a clean paper towel in the hood
keeping track of tubes and their respective caps.
6.9. Add 1.0 mL of TraceMetal Grade nitric acid and 250 uL of Trace Metal
Grade hydrochloric acid to each sample tube. Place the cap back on the
tube tightly and mix the contents of the tube by turning the tube several
times end on end. Vortex the glass tubes since some tend to leak when
inverted. Next place a fresh and clean paper towel in the hood next to the
heating block that will be used for heating the samples. Remove the caps
from the sample tubes and place the tube in the heating block while
keeping track and placing their exact respective caps on the paper towel
faced down.
6.10. Once on the heating block, close the Clean Box door and allow
approximately 30 minutes for the samples to reach 95° C*. Once they
have reached 95° C, heat for and additional 2.5 hours, or more (until there
is no further change in the appearance of the sample).
NOTE*: Place a thermometer in a culture tube filled with 50 mL of DI
water as a temperature monitor. Place this tube on the heating
block and remove at the same time as the samples.
6.11. After the heating is complete, remove the tubes from the heating block and
return the caps to the corresponding tubes. Do not tighten the caps and
allow the samples to cool for about 30 minutes. The samples may lose
some volume during the digestion. Bring the volume back to 50 mL with
DI water using the mark on the tube as a reference line.
6.12. Place the caps back on the sample tubes and mix the content. Vortex the
glass tubes since some tend to leak when inverted. The Teflon tubes can
be safely inverted 4-5 times for thorough mixing.
6.13. The samples are now ready for analysis. Write a tray number on a lable
and place the label on the handle of the sample rack. Place a colored dot
on the top of any sample tube that contains redigested samples. Make sure
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make a copy of it to turn to the analyst with the sample tray. Take the
samples and a copy of the water preparation logsheet to the metals lab. If
you are prepating redigestions make sure you enter the proper information
on the redigestion log. For regular routine samples insure that all the
sample status and the proper prepartion date and other information are
transfered to LIMS properly.
QUALITY CONTROL
NOTE: A digestion batch is defined as a set of twenty samples or less of the
same matrix group and dilution factor. The following matrices may be
grouped together in a batch.
1) W-FRH-FILT
2) W-GROUND, W-SURF-FRH, W-DRINKING
3) W-SURF-SLT
4) W-EFFLUENT, W-INFLUENT, W-OTHER
5) TCLP
7.1. Digestion Blank: One per twenty samples or less.
7.2. Duplicates: One set per digestion batch.
7.3. Sample Matrix Spikes
7.3.1. One set per each digestion batch.
7.4. Practical Quantitation Level (PQL): One per set of twenty samples or less.
7.5. Laboratory Fortified Blank(LFB): One per each analytical method per
spike type. For example a digestion tray with sample for ICP-TR and ICPMS
instruments will have LFB's representing spikes for all the spike types used on
that tray for ICPMS and also those used for the ICP-TR instrument.
SAFETY/HAZARDOUS WASTE MANAGEMENT
8.1. Treat all samples as a hazardous material by wearing gloves, safety
glasses, lab coats and following other pertinent safety guidelines.
8.2. The heating block should always be used in a fume hood.
8.3. Make sure the hoods are operating properly. In case of faulty hoods
contanct your supervisor and the laboratory safety staff as soon as
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9. REFERENCES
9.1. Metals Glassware Cleaning SOP, MT-006 (This SOP is currently under
revision, New name will be Cleaning Protocols for Preparation
Lab ware).
9.2. EPA Method 200.2, "Sample Preparation Procedure For Spectrochemical
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Appendix (A)
Preparation of QC Samples for Analysis of Metals in
TCLP extract, Water, Sediment, Tissue, and Waste samples
QC Stock Standards & Content (amount used for 50 ml of digestate in ml):
A) Practical Quantitation Limit Sample(s):
W-ICP-23 PQL
Contains all metals analyzed by the ICP-AES instrument except Ag.
Ag PQL
Contains Ag only.
W-TRP-27 PQL
Contains all metals analyzed by the ICP-TR instrument.
W-ICPMS PQL
Contains all metals analyzed by the ICPMS instrument.(100 p.1)
GFAA PQL
Except for Cu, and occasionally Se we no longer analyze metals by this type of
instrument on routine basis. Consult the analysis group for obtaining new single
element PQL and SPIKE stock solutions for the analyte of interest.
TCLP FLAME PQL
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B) Spike Solution(s):
Water Snike Mix A contains elements: Al, Sb, Be, B, Cd, Cr, Fe, Mn, Ni, Sr, V
Water Spike Mix B contains elements: As, Ba, Co, Cu, Pb, Mo, Se, Ti, Sn, Zn
Water Ag Spike : contains Ag only.
Mineral Spike contains: Al, Ca, Fe, Mg, K, Na
Cu GFAA Spike: contains Cu only.
UN1VSED Spike: Contains 24 elements: Sb, As, Ba, Be, Cd, Cr, Co, Cu, Mn, Mo, Ni,
Se, Ag, Sr, Tl, Sn, V, Zn, Al, Ca, Fe, Mg, K, Na
Ti and B : are not present in UNIVSED spike solution. They are prepared
as single element spike. Consult the analytical group for the amount
required to obtain the required spike concentration.
Sediment Ag Spike: contains Ag only:
Analytical tests and their corresponding QC samples
(*Note : All added volumes are 1 ml unless otherwise noted.)
- At times a sample may need to be spiked at LOW and HIGH levels. You are
notified in such cases by the analyst and/or supervisor and the comments in the
Redigcstion log,.
Water
PQL: For each instrument, ICP-AES, ICP-TR, and ICPMS use the corresponding
PQL solution.
SPIKE: For all three instruments:
- For all metals except Ag and Minerals use Water Spike Mixes A and B
- For Ag use Ag Water Spike solution
- For Minerals use the Mineral Snike solution
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Cu-MIBK
PQL: Use Cu GFAA Spike solution (100 ul)
Spike: Use Cu GFAA Spike solution (500 ul), One level of spike only.
- At times a sample may need to be spiked at LOW and HIGH levels. You are
notified in such cases by the analyst and/or supervisor and the comments in the
Redigestion log,.
TCLP
PQL: Use TCLP FLAME POL for Glass (50 ul)
Spike: For all elements except Ag and Minerals use UNIVSED Spiking
solution (100 uI/500 ul)*
For Ag Use Ag Sediment Spike (100 ul/ 500 ul)*
Minerals are not on the TCLP list and therefore are not accounted for in this
type of analysis and preparation.
*Note: Spike the samples for this analysis routinely at low and high levels. Use 100 jj.1
for LOW level spike and 500 jj.1 for HIGH level spike.
Sediments
PQL: A PQL QC sample is NOT prepared for sediment analysis.
SPIKE: For all elements except Ag use UNIVSED Spiking solution
For Ag use Ag Sediment Spike
Waste
PQL: A PQL QC sample is NOT prepared for sediment analysis.
SPIKE: For all elements except Ag use UNIVSED Spiking solution (2 ml)
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Tissue
PQL: A PQL QC sample is NOT prepared for sediment analysis.
SPIKE: For all elements except Ag use UNIVSED Spiking solution (200 ul)
For Ag use Ag Sediment Spike Solution (200 ul)
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yy?r
Author: Jack Martin
Revision Date: 02/17/97,5/10/1998
Editor: K. Barrett, M. Emad
MT-002-2
MICROWAVE DIGESTION OF SOIL, SEDIMENT, TISSUE AND WASTE SAMPLES
FOR TOTAL RECOVERABLE METALS ANALYSIS
(EPA Method 305181 Modified)
(Specific to the CEM Microwave Digestion System Model 2100)
1. SCOPE AND APPLICATION
1.1. This method details the digestion of soil, sediment, tissue and waste samples by
microwave oven for total recoverable metals. This method is a modification of
the EPA method 3051,81
1.2. Digested samples produced by this method are suitable for analysis by Inductively
Coupled Plasma Atomic Emistion Spectrophotometer (ICP-AES), Inductively
Coupled Plasma Mass Spectrometer (ICP-MS) and Graphite Furnace Atomic
Absorption spectrophotometer.
2. SUMMARY OF THE METHOD
2.1. A representative sample (minimum of 0.5g dry matter) is digested by means of a
microwave in (1) nitric acid and hydrochloric acid for ICP analysis or (2) nitric
acid followed by an additional digestion with hydrogen peroxide for GFAA
analysis. A separate aliquot of the sample is dried for Percent Solid
8 2
determination .
3. APPARATUS AND EQUIPMENT
3.1. Eppendorf 1000 uL pipette.
3.2. Ohaus GT-410 toploading balance.
3.3. CEM Microwave Digestion System Model MDS-2100.
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3.3.2. Digestion Vessels: Designed to contain sample, reagents and spiking
solutions in a high temperature, high pressure environment. The specific
components include:
3.3.2.1. Teflon Vessel Liners: Directly contain the sample, reagents and
spiking solutions.
3.3.2.2. Rupture Discs: Thin Teflon (PFA) discs designed to fail at 200
psi, preventing dangerous build-up of pressure within the vessel.
3.3.2.3. Inner Vessel Cap: Teflon cap designed to cap and seal the vessel
liners. They are connected to vent tubes that direct sample and
reagents into a reservoir in the event a rupture disc fails under
excessive pressure.
3.3.2.4. Outer Vessel Jacket: Teflon/Kevlar composite jacket designed
to contain the other vessel components safely in the high pressure
environment.
3.3.2.5. Outer Vessel Cap_: Heavy duty plastic screw cap designed to
seal the inner vessel cap and the vessel in the high pressure
environment.
3.3.2.6. Control Vessel Sensor Head: Consists of a pressure monitor
probe.
3.3.2.7. Microvave transparent pressure line valve: allows the sensor
vessel assembly to be removed while the internal pressure is still
high. Thus a subsequent digestion can be performed
immediately.
3.3.2.8 Fiberoptic temperature probe with Teflon coated thermowell: for
temperature monitoring and control during digestion. Note: the
control vessel must be fitted with an open ferrule nut to use the
temperature probe.
3.3.3. Oven Carousel: Holds 12 digestion vessels and the overflow reservoir.
3.4. Stainless Steel Spatulas.
3.5. Polypropylene 100 mL volumetric flasks.
3.6. Polyethylene Funnels.
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3.7. Wooden 6-space Filter Rack:.
3.8. Aluminum and polystyrene weigh boats.
4. REAGENTS AND CHEMICALS
4.1. Deionized water (DI water).
4.2. Concentrated Trace Metal grade Nitric Acid (TMG HNO3).
4.3. Concentrated Trace Metal grade Hydrochloric Acid (ICP only).
4.4. 30% Hydrogen Peroxide. (For analysis by graphite furnace only)
4.5. Aqua Regia (a 1:3 mixture of Reagent grade Nitric acid and Reagent grade
Hydrochloric acid solution respectively): Place a 4 L beaker inside a plastic
bucket in the hood. In the 4 L beaker add 1 L of nitric acid to 3 L of
hydrochloric acid.
NOTE: Always list Lot Number and the name of chemical suppplier of
all reagents on the digestion sheet.
4.6. Standards and Spiking Solutions:
4.6.1 SPIKING AND PQL SOLUTION(S):
Are prepared by the Analysis group. Inform the supervisor of the Analysis
and the Inorganic Preparation Group when the prepared stocks are either
close to expiration, as inidicated by label on the bottle, or about to run out.
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4.6.2 See Appendix (A) for details.
Sample type Univ. Spiking solution Ag Spiking sltn. Min Spiking solution
Sediment 1 ml 1 ml 2 ml
Tissue 200 ul 200 ul 500 ul
Waste 2 ml 2 ml 1 ml
4.7. 3.5% Nitric Acid: Add 50 mL concentrated Trace Metal Grade HNO3 to
1950 mL DI water (a 1:20 dilution).
5. SAMPLE COLLECTION, PRESERVATION, AND HANDLING
5.1. Solid samples do not require preservation other than storage at 4°C. There is no
established holding time limitation for solid samples. Solid samples for metals
analysis are stored in the either Refrigerator #4 or #5. Other matrices are stored
in the metals room at room temperature.
5.2. All labware should be cleaned according to the SOP for Cleaning Protocols for
Preparation Labware.8 4
6. SAMPLE PREPARATION PROCEDURE
6.1. Log the samples out from the receiving room and set aside to allow to come to
room temperature.
Obtain the needed number of clean digestion vessel liners and inner caps.8,4
6.2. Obtain the needed number of clean digestion vessels and inner caps as well as a
pressure sensor head. For cleaning instructions refer to the SOP for Cleaning
8 4
Protocols for Preparation Labware.
6.3. Replace the rupture disc in each cap assembly.
6.5. Print out sample labels and place each on the outside of a digestion vessel jacket
before placing the vessels into a carousel.
6.6. Weighing Out Samples:
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NOTE: The samples are weighted directly inside the liners. Per EPA method 3051 up to
0.500 g of sample by dry weight may be digested for analysis. Tissue and waste samples
are prepared as wet samples. A dry weight determination is not required for these
matrices. For liquid wate a known volume of sample is weighed and the density of the
sample is calcuated. Based on the density value a volume of the liquid waste equal or
less than 0.500 g of sample is used for analylsis.
Dry weight is obtained by determining the percent solid for each sample and must be
reported on the preparation sheet. This measurement must be determined prior to the
8 2
digestion of the sample '
6.6.1. Dry the inside and outside of a liner and cap assembly and weight to the
nearest 0.01 gram.. Remove the outer and inner caps and tare the balance.
6.6.2. Dispensing sample to the digestion vessel: Before addition of the sample
into the liner the sample must be thoroughly mixed and homogenized.
Eventhough this state is accomplished during the percent solid
8 2
determination mix the sample again prior to digestion within the
sampling container before placing inside the liner. Due to the versatile
nature of samples received for this preparation the following steps are
guides to follow depending on the nature of the sample received.
6.6.2.1. Slurry sample: a separation is evident between loose, wet sand
and the water layer and is easily mixed. Mix the sample
thoroughly with a stainless steel spatula until homogeneous.
6.6.2.2. Paste sample: organic matter is obvious in the sample. The
sample has enough moisture in it to create a paste when mixed.
Remove any rocks, shells, twigs, etc. Mix thoroughly with a
stainless steel spatula.
6.6.2.3. Sand sample: loose, dry sediment/soil that needs minimal
breaking up of large particles. Mix thoroughly, breaking up any
clumps of sand. A mortar and pestle can be used.
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6.6.2.4. Clay sample: dry, hard, compacted sediment that requires
crushing of particles. Mix thoroughly. A mortar and pestle can
be used.
6.6.3. Weigh enough of homogenized sample (approx. 0.5 - 1.0 grams) into the
vessel liner which will result about 0.5 gram of dry matter. Record the
weight to the nearest 0.001 gram.
6.6.4. Loosely replace the cap and place the liner into the corresponding
vessel jacket. Place the entire digestion vessel assembly into the •
carousel.
6.6.5 The sample in the sensor vessel will not be analyzed. Choose the
sample that is likely to be the most reactive and weigh out as much as
the highest sample weight in the other vessels. The system will
monitor pressure/temperature from this sample, so it should be one
that will generate the most pressure in the set. The weights for the
vessel and sample are not recorded.
6.7. Quality Control Samples
6.7.1. Digestion Blank: One per digestion of 20 samples.
6.7.2. Sample Duplicate: One set of duplicate sample per digestion batch to
botain precision data.. In general use the same sample used for matrix
spikes except when notified otherwise.
6.7.3.
6.7.3.1 Sample Matrix Spikes(See Appendix A for details):
Spiked a sample and its duplicate: 2 spikes of the same sample for
accuracy and precision determination
Mineral Spike: one of if needed
6.7.3.2 Laboratory Fortified Blank(LFB): One per each analytical
method per spike type. For example a digestion tray with samples
for ICP-TR and ICPMS instruments will have LFB's representing
spikes for all the spike types used on that tray for ICPMS and also
those used for the ICP-TR instrument.
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NOTE: A digestion batch is defined as a set of 20 samples or less of the same
matrix group. The possible matrix groups that can be presented by their one
corresponding spike are as follows:
1. S-SOIL Soil
S-FRHWTRSD Fresh Water Sediment
2. S-MARINESD Marine Sediment
S-OTHER Any soil/sediment not in the above
3. WAS-AQ Aqueous Waste
WAS-NONAQ Non-Aqueous Waste
WAS-SOL Solid Waste
WAS-OTHER Any waste not in the above
All samples in the same matrix group are digested in the same batch. If
there are >20 samples of the same matrix group then batcheach twenty
samples together and digested accordingly together. Each batch requires
its own set of quality control samples.
6.7.4. Selecting Samples for Quality Control
6.7.4.1. Randomly choose a sample to be used as the quality control
sample(s). This sample will be prepared with a duplicate, and
the appropriate spikes for the analysis being performed. Thus 4
to 5 repliate of this one sample will be weighed out depending on
the analysis and components requested.
6.7.4.2. To the weighed out sample add the appropriate Spiking
Solutions as dictated by the particular analysis.(See Appendix A)
6.7.4.3 Choose the appropriate spiking solution corresponding to the
analyte. Record on the preparation logsheet the amount of each
spiking solution added, the preparationdate of the spiking
solution and its preparer. Each spiking solution must have an
expiration date on its label. This information must also be
relfected on the preparation log. For the Mineral Spiking
Solution record the amount and its lot number as well as the
epiration date of the stock as indicated on the bottle. This
spiking solution is used as purchased.
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6.9. The addition of all acids should be performed under a fume hood. Slowly add
10 mL of Trace Metal Grade nitric acid to each vessel liner. Caution: Beware of
possible violent reaction with certain matrices. If foaming occurs gently swirl the
liner to break up the bubbles.
6.10. Next slowly add 5 mL of Trace Metal Grade hydrochloric acid to each vessel
liner. Again beware of reactive nature of some samples. Do not add HCI to
samples to be analyzed by graphite furnace since chloride ion interferes with
this analysis.
6.11. Reassemble each liner cap and outer cap loosely and leave vessels inside the fume
hood.
6.12. -Allow the samples to sit for a minimum of 1 hour or until minimal reaction is
observed. For highly reactive samples tighent the assembly caps and place the
digestion vessel(s) on the orbital shaker for as long as necessary to reduce
foaming and other reactivity (very reactive samples may need to be shaken
overnight). Periodically loosen the caps to release the build up pressure. It is
desirable to allow the samples to react as much as possible and to release as much
gas as possible prior to subjecting them to the high pressure environment in the
microwave (this lessens the chance of blowing a rupture disc during the
digestion). After the samples have sat or have been shaken re-tighten the caps
and re-weigh each sealed liner/cap assembly and record the weight to the nearest
0.001 gram and place in the carousel. Arrange the vessels symmetricaly in the
carousel.
6.13. Fill the 60 cc syringe connected to the pressure sensor module with DI water.
Turn the 3-way valve to the Backflush position and inject the water through the
pressure sensor tubing into a beaker. Repeat until the water pouring into the
beaker is clear. Leave approx. two inches of air at the end of the tubing. Turn the
3-way valve back to the Neutral position.
6.14. Insert the end of the pressure sensor tubing into the receptacle of the line valve
and the tubing from the other end of the valve into the sensor module. Hand
tighten the plastic retaining nuts.
6.15 Insert the fiber optic temperature probe into the thermowell of the sensor head,
until the phosphor tip contacts the bottom of the thermowell. Exercise care when
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handling the temperature sensor since it is very fragile. Secure the pressure sensor
tubing and the temperature probe in the stem notch of the overflow reservoir.
Place the carousel into the oven and close the door.
6.16. Programming the Oven for Digestion.
6.16.1 Turn on the oven. The Liquid Chrystal Display (LCD) will show a startup
menu:
fl - SYSTEM SETUP
f2 - PROGRAM NEW METHOD
f3 - RECALL METHOD/DATA
f4 - USEPA METHODS
For "normal" samples that do not exhibit excessive reactivity (after pre-
digestion), The standard EPA 3051 method is used. Press f4 to display the
list of EPA methods:
1 —> NDPES
2 —> SW-3015 (TEMPERATURE)
3 „_> SW-3015 (PRESSURE)
4 ...> SW-3051 (TEMPERATURE)
5 ...> SW-3051 (PRESSURE)
6 —> USEPA POWER CALIBRATION
In general the time-to-temperature- method is desired (#4) since it will
reach the correct temperature as dictated by the method. If, however, it is
suspected that the samples will build excessive pressure during digestion
the time-to-pressure method (#5) may be used, (the 3015 methods are for
water samples).
Both options have a 5.5 minute ramp to reach the programmed
temperature/pressure and a hold time of 4.5 minutes.
6.16.2 User Defined Methods — utilized for waste samples, tissue samples,
sediment samples with a high organic content or marine sediments.
A previously stored user method may be used, or a new one may be
programmed. To run a stored method press f3 — RECALL
METHOD/DATA. The display will show:
fl TO PRINT ALL PROGRAMS
"LIST OF PROGRAMS"
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Press the down arrow key to scroll through the programs until the desired
one is highlighted. Press ENTER to access the Load screen, which will
display:
fl - LOAD PROGRAM
f2 - ERASE PROGRAM
f3 - PRINT PROGRAM
Press fl to load the program. The Operations screen will display:
OPERATING PARAMETERS LOADED
fl - SAVE f2 - MENU
O - REVIEW f4 - START
Press D to review operating parameters. The next screen will display the
power, temperature, pressure and time parameters for each digestion stage.
Press f2 - next to access the next screen, which will display:
FAN 100 100 100 100 100
VESSELS 0 ACV VESSELS
VOLUME per VESSELS 15 ml
SAMPLE WEIGHT l.Og
ACID NITRIC HCL
The only field that needs to be changed is number of vessels. Scroll down
to the "0" and enter the total number of vessels on the tray (including the
sensor vessel).
Press f3 - END to return to the operations screen. Press f4 - START to
begin the digestion.
If none of the stored methods is suitable for the samples a new digestion
method may be programmed. See page 64 of the CEM operation manual
for instructions on method programming.
6.17. After the digestion is complete remove the vessels from the oven and place under
a fume hood to cool. After cooling, again weigh each inner vessel, sample and
cap assembly and record the value to the nearest 0.01 gram under "after heat."
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Take caution while weighing since the samples will still be giving off fumes.
The weighing is performed to check for sample loss. If >10% of the liquidis lost
(not 10% of Total weight), there was a leak - repeat the digestion for that
particular sample. If this loss occurs in the blank, duplicates, or spikes the entire
batch should be redigested.
6.17.1 For samples to be analyzed by graphite furnace an extra digestion step is
required. After the samples have cooled, add 4ml of 30% H202 to each
vessel. If a strong reaction is noticable allow the samples to sit for a time
before heating. Use a program of 50 - 85 % power for 10 minutes,
depending upon the reactivity of the samples. Determine the percent
sample loss before this step.
6.17.2 Determine the total amount of sample loss with the following formula:
(Total Mass Before - Total Mass After)
% sample lost = 100% x -—
(Total Mass Before- Liner Mass)
6.18. Arrange for an adequate number of volumetric flasks (that have been previously
cleaned according to the SOP for cleaning)8-4 ancj plastic funnels to filter each
individual sample. Rinse the condensation on the inner Teflon cap into the
vessel liner with DI water by using a squirt bottle. Pour the contents of the
vessel liner into a volumetric flask and rinse the vessel liner with 3.5% HNO3
into the flask making sure that the entire content of the vessel including all of
the remaining solid is transfer'ed into the volumetric flaks.. Rinse the vessel at
least two more times with 3.5% HNO3. Bring the final volume of the samples
to 100 mL with DI water. Cap the flasks, invert 8-10 times and shake while
inverted to mix the sample completely.
6.18. The samples are now ready for analysis. Make sure that the group leader has
looked over the preparation log. Once initialled by both parites take the samples
and a copy of the preparation logsheets down to the metals lab.
7. SAFETY/HAZARDOUS WASTE MANAGEMENT
-------
7.1. Samples: All samples are handled as if they contain hazardous amounts of all
analytes (all metals except Mercury). Gloves should be worn at any stage
requiring contact with the sample. Excess sample should be disposed of in the
containers labeled Metals Waste w/o Hg. When full these must be emptied into
the large metals waste drums within 3 days.
7.2. Standards: Gloves should be worn when handling any of the spiking solutions.
Any excess spiking solutions should be disposed of into the containers labeled
Metals Waste w/o Hg.
7.3. Reagents: Gloves should be worn when handling any reagents (acids and H202).
Reagents should be added to samples in a fume hood with the sash lowered as far
as possible; both to reduce exposure to fumes and protect in case of splashing.
7.4. Used filters and dirty glassware: Gloves should be worn when handling any
filters or lab ware that have come into contact with samples and/or standards.
7.5. Filtered Sampled after Analysis: Gloves should be worn when handling the post-
analysis samples (even if no analytes were detected there are significant amounts
of acid present).All matrix spikes and samples with positive results for any
analyte should be disposed of into the container labeled Metals Waste w/o Hg.
All others can be poured down the sink.
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8. REFERENCES
8.1. EPA Method 3051, revision 0, November 1992.
8.2. Percent Solid Determination SOP, (Under final revision)
8.3. CEM MDS-2100 Operation Manual.
8.4. SOP for Cleaning Protocols for Preparation Labware
-------
Appendix (A)
Preparation of QC Samples for Analysis of Metals in TCLP
extract, Water, Sediment, Tissue, and Waste samples
QC Stock Standards & Content (amount used for 50 ml of digestate in ml):
A) Practical Quantitation Limit Sample(s):
W-ICP-23 PQL
Contains all metals analyzed by the ICP-AES instrument except Ag.
AgPQL
Contains Ag only.
W-TRP-27 PQL
Contains all metals analyzed by the ICP-TR instrument.
W-ICPMS PQL
Contains all metals analyzed by the ICPMS instrumental 00 ml)
GFAA PQL
Except for Cu, and occasionally Se we no longer analyze metals by this type of
instrument on routine basis. Consult the analysis group for obtaining new single element
PQL and SPIKE stock solutions for the analyte of interest.
TCLP FLAME PQL
Contains all metals analyzed by the ICP-AES instrument.
-------
B) Spike Solution(s):
Water Snike Mix A contains elements: Al, Sb, Be, B, Cd, Cr, Fe, Mn, Ni, Sr, V
Water Spike Mix B contains elements: As, Ba, Co, Cu, Pb, Mo, Se, Ti, Sn, Zn
Water Ag Spike : contains Ag only.
Mineral Spike contains: AI, Ca, Fe, Mg, K, Na
Cu GFAA Spike: contains Cu only.
UNTVSED Spike: Contains 24 elements: Sb, As, Ba, Be, Cd, Cr, Co, Cu, Mn, Mo, Ni, Se, Ag,
Sr, Tl, Sn, V, Zn, Al, Ca, Fe, Mg, K, Na
Ti and B : are not present in UNIVSED spike solution. They are prepared
as single element spike. Consult the analytical group for the amount
required to obtain the required spike concentration.
Sediment Ag Spike: contains Ag only.
Analytical tests and their corresponding OC samples
(*Note : All added volumes are 1 ml unless otherwise noted.)
- At times a sample may need to be spiked at LOW and HIGH levels. You are notified in
such cases by the analyst and/or supervisor and the comments in the Redigestion log,.
Water
PQL: For each instrument, ICP-AES, ICP-TR, and ICPMS use the corresponding
PQL solution.
SPIKE: For all three instruments:
- For all metals except Ag and Minerals use Water Spike Mixes A and B
- For Ag use Ag Water Snike solution
- For Minerals use the Mineral Spike solution
(^Note : All added volumes are 1 ml unless otherwise noted.)
-------
Cu-MIBK
PQL: Use Cu GFAA Spike solution (100 ul)
Spike: Use Cu GFAA Spike solution (500 ul), One level of spike only.
- At times a sample may need to be spiked at LOW and HIGH levels. You are notified in
such cases by the analyst and/or supervisor and the comments in the Redigestion log,.
TCLP
PQL: Use TCLP FLAME POL for Glass (50 ul)
Spike: For all elements except Ag and Minerals use L'NIVSED Spiking
solution (100 ul/500 ul)*
For Ag Use Ag Sediment Spike (100 ul/ 500 ul)*
Minerals are not on the TCLP list and therefore are not accounted for in this type of
analysis and preparation.
*Note: Spike the samples for this analysis routinely at low and high levels. Use 100 ml for
LOW level spike and 500 ml for HIGH level spike.
Sediments
PQL: A PQL QC sample is NOT prepared for sediment analysis.
SPIKE: For all elements except Ag use UNIVSED Spiking solution
For Ag use Ag Sediment Spike
Waste
PQL: A PQL QC sample is NOT prepared for sediment analysis.
SPIKE: For all elements except Ag use UNIVSED Spiking solution (2 ml)
For Ag use Ag Sediment Spike (2 ml)
-------
Tissue
PQL: A PQL QC sample is NOT prepared for sediment analysis.
SPIKE: For all elements except Ag use UNIVSED Spiking solution (200 ul)
For Ag use Ag Sediment Spike solution (200 ul)
(*Note : All added volumes are 1 ml unless otherwise noted.)
-------
Revision: 04/24/98 by T.M. Chandrasekhar
Author: Bany Dupree
Editor: TMF
MT-019-2
DIGESTION OF SEDIMENT SAMPLES FOR TOTAL MERCURY ANALYSIS
SCOPE AND APPLICATION
1.1 This method details the digestion of sediment samples for total mercury content. This
method is applicable to soil, sediments, sludge and waste samples.
SUMMARY OF THE METHOD
2.1 In sediments, both organic and inorganic mercury can exist. In order to analyze for total mercury
content, the organic mercury must be converted to mercuric ions (Hg +2).
2.2. To accomplish this, each sediment sample is heated in hydrogen peroxide and nitric acid to
solubilise the sediment matrix. Then, the liquid sediment is heated with potassium permanganate
and potassium persulfate to completely oxidize mercury ions to Hg +2 state. Total mercury is
analyzed for as Hg +2
3. APPARATUS AND EQUIPMENT
3.1 125 mL High Density Polyethylene plastic bottles with cap
3.2 Fisher Scientific Isotemp Waterbath
3.3 Pipettes
3.3.1. 10-100 uL adjustable Eppendorf digital pipette
3.3.2. 100-1000 uL adjustable Eppendorf digital pipette
3.3.3. 1-5 mL adjustable Oxford Macro pipete
3.3.4. 5-10 mL adjustable Oxford Macro pipete
4. REAGENTS AND CHEMICALS
4.1. Optima grade Nitric Acid: If not in laboratory acid storage area, check the chemistry section's
acid storage room, order from chemistry receiving.
4.2. Trace Metal grade Nitric Acid: If not in laboratory acid storage area, check the chemistry section's
acid storage room, order from chemistry receiving.
-------
4.4. 5% Potassium Permanganate Solution: Add 25 grams, of permanganate crystals to a 500 mL
Nalgene bottle half full of deionized water and dilute to volume with deionized water and mix
well.
4.5. 5% Potassium Persulfate Solution: Add 12.5 grams, of potassium persulfate crystals to 250 mL
Nalgene bottle half full of deionized water and dilute to volume with deionized water. Mix well.
Prepare this solution each time digestion is performed. Do NOT store for later use.
4.6 Standards and Spiking Solutions
4.6.1 Commercial Stock Standard 1000 ppm: Commercially available inorganic mercury
stock, from SPEX, NIST, or BAKER
4.6.2 Stock Standard Solution 500 ug/L: Pipette out 0.100 (100 uL) of commercial 1000
ug/mL stock standard into a 200 mL volumetric flask filled half full with deionized water.
Add 1 mL of Optima grade nitric acid. Dilute to volume with deionized water and mix
well.
4.6.2 Stock Spike Solution 200 ug/L: Pipette out 0.100 mL (100 uL) of commercial 1000
ug/mL stock standard into a 500 mL volumetric flask filled half full with deionized water.
Add 1 mL of Optima or Trace Metal grade nitric acid. Dilute to volume with deionized
water and mix well. Prepared by metals analysts.
4.6.4 Marine Sediment Standard MESS-2 (0.092 ug/g): Commercial available dry marine
sediment standard from Canadian Research Council. Store in a desiccator in laboratory.
NOTE: Record all reagent and spiking solutions on the prep sheet and in the reagent prep logs.
SAMPLE COLLECTION, PRESERVATION, AND HANDLING
5.1 All equipment and glassware should be scrupulously clean to avoid contamination: refer to SOP
9 1
on Cleaning Protocols for Cleaning Labware.
5.2 All sediment samples are stored in the metals room in the receiving room of the DEP laboratory.
SAMPLE PREPARATION PROCEDURE
6.1 Turn on water bath in sample digestion room and set temperature to 95° C on control panel. Fill
water bath with deionized water up to the fill mark on the bath. Replace water in water bath
weekly.
6.2 Prepare sample digestion bottles by cleaning the disposable digestion bottles following the SOP
for Cleaning Protocols for Preparation Labware. The digestion bottles and their respective caps
should be thoroughly cleaned.
6.3 Remove 30% Hydrogen Peroxide (H202)from the refrigerator so that it may come to room
temperature.
6.4
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6.4.1 Label the bottom of an empty disposable aluminum weigh boat with sample number and
current date. For each sample, weigh the empty boat and record the value in the
sediment logbook. This is the tare weight. Tare the balance. Place approximately 10
grams of thoroughly mixed sediment into the weigh boat. Record the weight for the
sediment exactly. Repeat for each sample in the set.
6.4.2 Place samples plus weigh boat into drying oven (103-105° C) for a minimum of 24
hours. Remove samples from the oven and allow to cool in a desiccator for about 1 hour.
Carefully weigh each sample and record the weigh exactly. Subtract the weight of the
aluminum boat from both the wet and dry weights. Percent Moisture can be determined
by the following calculation:
dry wt
Percent Solid = X 100
wet wt
The dry weight of the sample digested must be determined by the following calculation:
dry wt
dry weight of sample = X wet sample weight
wet wt
Note that if using the Hg-S Excel spreadsheet these calculations will be perfomed automatically as
the weights are entered into the proper fields.
6.5 Before transfering the sample into the digestion bottle, ensure all water has been shaken out of the
vessel. Wipe the outside of the vessel with a Kim-wipe if there is moisture on the outside. Place
the vessel on the top loading balance and tare the balance so that it is reading 0.000 grams. Using
a clean stainless steel spatula, carefully transfer approximately 1 gm of well-mixed sediment into
the BOTTOM of a pre labeled digestion vessel. Record the weight EXACTLY on the sediment
preparation logsheet. NOTE- Make sure NO sample has spilled onto the balance outside of the
beaker! Repeat for each sediment sample to be analyzed. When weighing replicate portions of
sample for the duplicates and spikes, take time to make sure that the sample weights are close
together!
6.6 Choose one sample that is NOT a trip blank, field blank or an equipment blank. Prepare a matrix
spike at 0.05 ug by adding 250 uL of 200 ug/L mercury spike to approximately 1 gram of sample
into a pre labeled culture tube. Record the sample weight EXACTLY. Prepare duplicate matrix
spikes for every 20 samples analyzed. NOTE: For Superfund samples, double the amount of
spike solution added.
6.7 Prepare a duplicate sample by weighing out approximately 1 gram of the SAME sample used for
the matrix spike into a pre labeled digestion bottle. Label this bottle with a B after the sample
number to distinguish it from its duplicate created in step four. Prepare one duplicate sample for
every twenty sample.
6.8 Prepare a marine reference standard by weighing out approximately 0.770-0.775 grams of MESS-
2 into a pre labeled culture tube. Record the weight the EXACTLY Prepare one MESS-2
reference for every 20 samples analyzed.
-------
6.9
Prepare a digestion blank by measuring out 40 ml of deionized water into a pre labeled culture
tube. Prepare 1 digestion blank for every twenty samples
6.10 Prepare a 0.010 ug PQL by adding 20 uL of 500 ug/L into a pre labeled culture tube filled with 40
ml of deionized water. Prepare 1 PQL for every 20 samples.
6.11 Add 5.0 mis of Trace Metal grade nitric acid to all sample vessels. Be careful of violent reactions
with the sediment matrices. If foaming occurs, gently tap the bottom of the tube to break foam
bubbles. Place the digestion blank and PQL vessels in an ice water bath for 10-15 minutes.
6.12 Add 2.0 mis of 30% hydrogen peroxide solution to all sample vessels including the chilled
digestion blank and PQL. Add the peroxide slowly to the digestion blank and PQL to prevent any
violent reaction. Allow the samples to react for at least 15 minutes.
6.13 For each vessel, tighten the cap and gently swirls the vessel. Quickly loosen the cap to vent the
built up gases. Repeat for all samples.
6.14 Loosen all caps and place in a 95° C water bath for 5 minutes. Carefully watch tubes for violent
reactions or foaming. Remove those tubes from water bath and tap to break foam bubbles. Return
to water bath and continue to watch.
6.15 Remove sample rack and allow to cool. Add 40 mis of deionized water to sediments and MESS-2
ONLY. DO NOT add 40 mis of water to standards, digestion blank or PQLs.
6.16 CAREFULLY add 10.0 mis of 5% potassium permanganate solution to all tubes. For all samples,
except the digestion blank and PQL, if the permanganate purple color does not persist for at
least 15 minutes, add sufficient excess 5% KMn04 to the tube in 1 mL increments until color
persists for at least 15 minutes. DO NOT ADD ANY EXTRA PERMANGANATE TO THE
DIGESTION BLANK OR THE PQL EVEN IF THE PURPLE COLOR OF THE
PERMANGANATE DISAPPEARS. There is excess oxidizer PRESENT in them. RECORD HOW
MUCH EXTRA PERMANGANATE SOLUTION HAS BEEN ADDED TO THE OTHER
SAMPLES.
6.17 Add 4.0 mis of 5% potassium persulfate to all tubes. Tighten Nalgene caps and gently invert the
culture tubes several times to mix. Loosen all caps and return samples to 95° C water bath for one
hour.
6.18 Cool samples and tighten caps. Samples can be stored for several days but should analyzed within
3 days.
NOTE: Record the concentrations, preparation dates and volumes of all standards and
spikes that you use in the comments section of the logbook. Xerox a copy of the logbook
pages and place it with the digested sample tubes. This will aid the analyst in performing
sample analyses and troubleshooting instrument problems.
QUALITY CONTROL
7.1. Digestion Blank: One per twenty samples.
-------
7.3. Duplicates: One set of duplicate sample per twenty samples
7.4. MESS-2 reference standard: One per twenty samples.
7.5. Practical Quantitation Level (PQL): One per set of twenty samples.
NOTE: Using these numbers, you can estimate how many sample tubes that you will need. The water
bath holds 40 sample tubes.
8. SAFETY/HAZARDOUS WASTE MANAGEMENT
8.1. Treat all samples as a possible hazard by wear appropriate laboratory clothing; gloves, safety
glasses, lab coat, etc..
8.2. The water bath should be placed in a well ventilated area.
8.3. All samples should be vented in a hood.
8.4. Watch for possible violent reactions when adding reagents to the digestion vessels. The addition
of reagents should be done in a well ventilated area.
8.5. The organic spike solution (methyl mercuric chloride) is hazardous and must be handled with
care. Be especially careful when handling the 1000 ppm stock solution for it contains traces of
organic solvents that mobilize mercury into biological tissues.
9 REFERENCES
9.1 MT-018-1, "Procedure for Mercury Glassware Cleaning".( The is SOP is currently under
revision, The new name will be SOP for Cleaning Protocols for Preparation Labware.)
-------
Revision: 04/24/98 by T.M. Chandrasckhar ty/f/f/? $7// J<2
Author: S. Minor, TMF yfLt /"/'^
MT-020-2 X
sWfles for tot,
DIGESTION OF WATER SAMPLES FOR TOTAL MERCURY ANALYSIS
1. SCOPE AND APPLICATION
1.1. This method details the digestion of water samples for the subsequent analysis for total mercury.
It is applicable to surface, saline, effluent, TCLP and waste waters.
2. SUMMARY OF THE METHOD
2.1. Organic and inorganic forms of mercury may be present in water samples. In order to perform the
total mercury analysis, all mercury compounds must be converted to inorganic mercuric ions (Hg
+2).
2.2. To accomplish this, the samples are oxidized in an acidic media with nitric and sulfuric acids.
Then the samples are further oxidized using potassium permanganate and potassium persulfate. It
is after the persulfate stage that all the mercury present in that sample has been converted to
mercuric ions. Total mercury is then analyzed for as Hg +2.
3. APPARATUS AND EQUIPMENT
3.1. Isotemp water bath
3.2. 75 mL Pyrex culture tubes and caps
3.3. 50 mL graduated cylinder
3.4. Innova 2100 platform shaker
3.5. Weigh boats
3.6. Mettler PE 360 balance
3.7. Pipettes
3.7.1. 50 uL Eppendorf
3.7.2. 100 uL Eppendorf
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5. SAMPLE COLLECTION, PRESERVATION, AND HANDLING
5.1. Samples are preserved with Nitric Acid.
5.2. All samples should be considered as hazardous. Wear gloves whenever handling the samples.
9 1
5.3. All glassware should be cleaned according to the SOP for cleaning mercury glassware. '
6. SAMPLE PREPARATION PROCEDURE
6.1. Fill water bath with deionized water up to the fill mark on the bath. Replace water in the water
bath weekly. Turn on water bath in sample digestion room and set temperature so that the samples
will heat at 95° C on control panel.
6.2. Water samples are digested in 75 mL Pyrex culture tubes. Make an exact count of the culture
tubes required for the digestion set, including all QC samples. The easiest way to do this is by
making the digestion worksheet. Record the concentrations, preparation dates and volumes of all
standards and spikes that you will be using in the comments section of the worksheet. After you
have made your digestion worksheet, make a LIMS worksheet of the samples that you will be
digesting. This aids others by letting them know which samples you are doing. Also, it is easier
to make labels from a LIMS worksheet. Prepare the necessary labels with any dilution, spike
information, etc. included on the labels. Record the concentrations, preparation dates and volumes
of all standards and spikes that you will be using in the comments section of the worksheet.
6.3. Prepare sample digestion tubes by putting the labels on them and discarding the Bromine
Monochloride cleaning solution that has been stored in the glassware. The Bromine Monochloride
should be dumped in the sink and flushed thoroughly with water. The glassware should then be
rinsed 6-8 times with deionized water. When rinsing, fill the tube with DI and pour this DI over
the inside of the cap. After rinsing the tube 6-8 times, replace the cap on the tube, leaving the tube
empty.
6.4. Prepare a digestion blank by measuring out 50 mis of deionized water into a pre labeled culture
tube. Prepare 1 digestion blank for every 20 samples digested.
6.5. Prepare a 0.2 ug/L PQL by adding 50 uL of 200 ug/L into a pre labeled culture tube filled with 50
of deionized water. Prepare 1 PQL for every 20 samples.
6.6. Prepare an N1ST reference standard at 3.0 ug/L by adding 3 nils of 50 pg-'L NIST 3133 check
standard to a pre labeled culture tube. Dilute with 47 nils of deionized water to a final volume of
50 ml. Prepare one EPA check standard for every 20 samples analyzed.
6.7. Shake each sample bottle several times to homogenize any precipitated sample particles.
Carefully measure out 50 mis of thoroughly shaken sample into the respective labeled culture
tubes using a clean, acid rinsed 50 ml graduated cylinder. After transferring each sample to the
tube, rinse the graduated cylinder once with 1:1 Nitric and 4-5 times with DI water. When
pouring up the duplicates and spikes, shake the sample well in between each sample that is poured.
6.8. Choose a sample that is NOT a trip blank, field blank or an equipment blank with which to prepare
a sample duplicate, the sample matrix spike, and its duplicate. The labels for this sample should
-------
8.2. Gloves should be worn when handling any of the PQL, spiking solutions, or reference standard.
Any excess spiking solutions should be disposed of into the containers labeled Metals Waste with
h8-
8.3. Gloves should be worn when handling any reagents. Reagents should be added to samples near
the slot hood.
9. SAMPLE ANALYSIS
Refer to SOP MT-011-2, "Analysis of Total Mercury in Water by Cold Vapor Atomic Absorption
Spectroscopy" for analysis details.
10. APPENDIX - TCLP SAMPLES
TCLP extracts are digested similarly to waters with a few exceptions. TCLP extracts are diluted 1/10,
using 5 mLs TCLP extract and 45 mLs DI. Also, TCLP extracts represent a different batch, requiring
separate duplicates and spikes. These spikes are made using the same amount of Hg spike solution as a
normal water spike. However, one PQL, Blank, and NIST 3133 can be shared by all batches. Be sure to
note which samples are TCLP extracts on the digestion sheet and the dilutions.
11. REFERENCES
11.1. MT-018-1, "Procedure for Mercury Glassware Cleaning".
-------
Revision date: 4/16/98 £~'/2 ^
Revised by: Rob Hudson, Chris Morgan and Robert Pellow
MT-046-1
Analysis of Selected Metals by Inductively Coupled Argon Plasma-Atomic Emission Spectroscopy
(ICAP 61 Enviro Trace Purge Spectrometer)
1. SCOPE AND APPLICATION
1.1. This method details the analysis of metals in waters, soils, wastes and other environmental
samples utilizing an Inductively Coupled Argon Plasma - Atomic Emission Spectrometer, ICAP
61 Enviro Trace Purge Spectrometer.
1.2. The Thermo Jarrell Ash ICAP 61E Trace Analyzer is an atomic emission instrument using an
inductively coupled plasma as the excitation source and a polychrometer as the detector. It is
capable of accepting up to 63 channels simultaneously. The plasma provides a high degree of
excitation and is very stable over long periods of time. As a result the chemical interferences of
the sample matrix are reduced and the plasma exhibits a linear dynamic range of 4-6 orders of
magnitude. Axial viewing of the ICP torch improves the observed emission intensity resulting in
an improved signal to noise ratio and lower detection limits than routinely obtained with a radial
instrument. There are 27 elements analyzed simultaneously in the current instrument setup.
This method is based on EPA Method 200.7 for water samples and EPA method 6010 for solid
and waste samples.
2. SUMMARY OF METHOD
2.1. Digested water, sediment, waste and tissue samples are analyzed and reported as 'total
recoverable metals'. Filtered water samples are analyzed without digestion and reported as
'dissolved metals'. TCLP (Toxic Characteristic Leaching Procedure) and SPLP (Synthetic
Precipitate Leaching Procedure) samples are also analyzed. Soils and sediments are reported on a
dry weight basis; wastes and tissues are reported on a wet weight basis.
2.2. The table on the following page lists the 27 elements currently analyzed, along with the spectral
line (angstroms) and calibration limit of each.
2.3 Implementation of an Internal Standard for ICAP 6 IE Trace Analysis. Axial viewing of the ICP
torch allows cooler zones of the plasma to be observed. Matrix interaction with the emission
excitation processes can change the emission signal. The presence of analytes at high
concentrations can cause a supression of other analyte intensities. Another common form of
physical interference is the supression of analytical signals in samples with high voscosity.
To enhance stability with respect to these physical effects, an internal reference standard (Y) is
used when that element is not present in the samples.
2.4 To compensate for the ionization effect of analytes with low ionization potential, a 200 ppm Li
solution is added to all samples and standards.
-------
Revision date: 4/16/98
Revised by: Rob Hudson, Chris Morgan and Robert Pellow
MT-046-1
3.7. The rinse water supply pump tubing is 1.14 mm ID, 3 collar tygon pump tubing - Red/Red/Red -
Cole-Parmer - Cat. No. 95600-30.
3.8. The internal standard pump tubing is 0.38mm ID, 3 collar tygon pump tubing -
Orange/Green/Orange - Cole-Parmer - Cat. No 95600-14.
3.9. Two tanks of liquid Ar (ordered from Air Products) are required. One tank is used for the
formation and support of the plasma, sample introduction and purged optical path (POP). The
second tank provides an inert gas atmosphere (primarily by removing oxygen) for the entire
optical system, PMTs and channel cards of the spectrometer.
4. REAGENTS AND CHEMICALS
Note: Be careful not to contaminate solutions with metals or minerals during preparation and use. Be
sure to mix all solutions thoroughly immediately after they are prepared. Store standard solutions in
Teflon bottles. Information about Stock Standards are listed in APPENDIX A. Pipets used in the
preparation of standards, SRMs and spiking solutions must either be glass volumetric pipets or
Eppendorf type pipets. If Eppendorf pipets are used, their calibration must have been rechecked within
one month prior to use. Eppendorf pipets must be calibrated/rechecked using a balance that has been
calibrated with an NIST traceable weight set on the day the balance is used.
4.1. Reagents -
4.1.1. De-ionized water - from Laboratory D.I. water supply system.
4.1.2. Optima grade nitric acid.
4.1.3. Trace metal grade hydrochloric acid.
4.1.4. Rinse Water- DI water.
4.1.5. Acid Rinse Solution - Dilute 100 mL OPTIMA nitric acid and 50 mL of Trace Metal
Grade HC1 to 1000 mL with D.I. water - this solution contains 10% HN03 and 5% HC1.
4.1.6. As Profile Solution - 5 ppm As solution: Pipet 5 mL of SPEX 1,000 mg/L As solution
into a 1000 mL volumetric flask containing 500 mL of D.I. water, 20 mL of OPTIMA
nitric acid and 10 ml Trace Metal Grade HC1. Dilute to the mark with D.I. water.
4.1.7. A1 Profile Solution - 5 ppm A1 solution: Pipet 500 |ri of SPEX 10,000 ppm A1 standard
into a 1000 mL volumetric flask containing 500 mL of D.I. water, 20 ml of OPTIMA
nitric acid and 10 ml Trace Metal Grade HC1. Dilute to the mark with D.I. water.
4.1.8 Internal Standard Solution - 1000 ppm Li and 5 ppm Y solution: Weigh 5.3 g of 99.99%
lithium carbonate and slowly add to a 1000 ml volumetric flask containing 500 ml DI
water, 20 ml OPTIMA nitric acid and 10 ml Trace Metal Grade HC1. Pipet 0.500 ml
SPEX 10,000 ppm Y standard into the volumetric flask and dilute to the mark with DI
water.
-------
Revision date: 4/16/98
Revised by: Rob Hudson, Chris Morgan and Robert Pellow
MT-046-1
4.4.3 AG250C - 250 ppb Ag - Ag calibration verification solution. Pipet 250 p.1 Spex 1000 ppm
Ag stock standard into a 1000 ml volumetric flask containing 500 ml DI water and 20 ml
OPTIMA nitric acid. Dilute to the mark with DI water.
ICS2007 Working Stock 1 - Pipet 2 mL of ICS200.7 Stock 1 and 2 mL of ICS200.7
Stock 2 (refer to APPENDIX A) into a 200 mL volumetric flask containing 100 mL of
D.I. water and 1 ml of OPTIMA nitric acid. Dilute to the mark with D.I. water.
ICS2007 Working Stock 2 - Pipet 2 mL of ICS200.7 Stock 3 (refer to APPENDIX A)
into a 200 mL volumetric flask containing 100 mL of D.I. water and 1 ml of OPTIMA
nitric acid. Dilute to the mark with D.I. water.
ICS2007 - interference check solution. Pipet 50 mL of ICS200.7 Working Stock 1, 50 mL
of ICS200.7 WorkingStock 2, and 10 mL of ICS200.7 Stock 4 (refer to APPENDIX A)
into a 500 mL volumetric flask containing 250 mL of D.I. water and 5 ml of OPTIMA
nitric acid and 5 ml Trace Metal Grade HC1. Dilute to the mark with D.I. water.
4.5. POL and Spiking Solutions -
4.5.1. Instrument POL solution - IPQL-T1- Prepared from individual element Spex stock
standards in 2% OPTIMA nitric acid and 1% Trace Metal Grade HC1. The current PQLs
may be found in G:\Qccalc.2\metals\Icp-trac\Mdl_pql.dat.
4.5.2. Digestion POL Spike Solution - DPQL-T1 - Prepared from individual element Spex stock
standards in 2% OPTIMA nitric acid and 1% Trace Metal Grade HC1. The current PQLs
may be found in G:\Qccalc.2\metals\Icp-trac\Mdl_pql.dat.
4.5.4. Metal Water Spike Solution - HI1+2+AG - Prepared from individual element Spex stock
standards in 2% OPTIMA nitric acid and 1% Trace Metal Grade HC1. The Ag spike
solution is prepared separately from the other analytes. Refer to Appendix B
4.5.5. Mineral Spike Solutions - MIN-LOW and MIN - Prepared from Spex XFER-1. Refer to
Appendix B.
4.5.6. Metal Sediment Spike Solution - UNIVSED - Prepared from individual element Spex
stock standards in 2% OPTIMA nitric acid and 1% Trace Metal Grade HC1. Refer to
Appendix B.
4.5.8. Instrument Mineral Spike Solution - MIN - Prepared by diluting Spex XFER-1 (80/200).
Refer to Appendix B.
4.6. Interelement Correction (IEC) Checking Solutions - Each IEC checking solution listed below is
prepared and analyzed twice, but each time from the stock of a different vendor (Primarily SPEX
and INORGANIC VENTURE- refer to APPENDIX A) Contaminants in the stock of one
vendor are in this way identified.
4.6.1. Fe 200 ppm Solutions - Pipet 2 mL of 10,000 ppm Fe stock standard into a 100 mL
volumetric flask containing 50 mL of D.I. water and 500 uL of OPTIMA nitric acid,
dilute to mark with D.I. water.
4.4.4.
4.4.5.
4.4.6.
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higher concentration solution for spiking. The maximum spike level is determined by the
concentration of analyte in the sample and the upper limit of the calibration curve.
SAMPLE ANALYSIS PROCEDURE
Note: Read ICAP 61E Trace Analyzer Operator's Manual provided by TJA before proceeding.
6.1. Turn on the COMPUTER and load the ThermoSpec software by typing I in the directory of
C:\station\run\bin followed by Enter. If ThermoSpec is already loaded, go back to the Main
Menu by pressing Esc until the screen which has the words Main Menu is shown in the top right
hand corner.
6.4. Pre-Check the followine:
6.4.1. Connect pump tubings -Make sure that pump tubings are not flat or have visible damage.
If necessary, change them.
6.4.2. Rinse water level - The rinse water should be at least one-quarter full. If it is not, prepare
more (see 4.1.4) .
6.4.3. Ar gas pressure - The regulator setting should be at 60 psi during Ar flow. If the pressure
falls below about 50 psi, a safety interlock automatically turns off, and the plasma torch
cannot be lighted.
6.4.4. Liquid Ar level - Ensure that there is adequate liquid argon for the analysis:
6.4.4.1. The Ar tank for the formation and support of plasma, sample
introduction, and for the POP should be at least one half full.
6.4.4.2. The Ar tank should be at least one third full for the formation of inert gas
atmosphere for the entire optical system, PMTs, and channel cards of the
spectrometer
6.4.5. The nebulizer and the mixing chamber - Check the Meihardt concentric glass nebulizer to
be sure it is clean and produces a smooth mist. The mixing chamber needs to be cleaned if
it develops oily film deposits, the sample should drain smoothly from the sides of the
chamber. For cleaning instructions read ICAP 61E Trace Analyzer Operator's Manual,
section 'Maintenance'.
6.4.6. The torch - The plasma torch must be cleaned whenever salt deposits begin to clog the
central sample tube orifice, or whenever metallic deposits cause elevated and non-reliable
blank readings. The torch disassembles into two parts, one comprised of the outer and
intermediate tubes mounted to the ceramic base, and one comprised of the sample tube.
The torch can be cleaned without disassembling. To remove salt deposits, wash the torch
in ultrasonic bath for a few minutes using soapy water. To remove metallic deposits from
the sample introduction tip, dip the tip into hot aqua regia. After cleaning, rinse the torch
copiously with D.I. water and dry thoroughly. CAUTION: Avoid getting the ceramic
base wet if possible and avoid immersing the base in the ultrasonic bath as the ultrasonic
vibrations may cause the epoxy seals to beak down and separate. Also extended exposure
to acids may damage the epoxy seals in the torch.
6.4.7. The. cooler - Ensure that the power is on, the temperature setting is 24 C, the water
pressure is 40 psi and there is enough water for cycling. If water level is low, a safety
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MT-046-1
6.5.4.5. Pump Rate: The peristaltic pump rate may be adjusted from 0 to 200 rpm.
It is advisable to set to 110 rpm for analysis.
6.5.5. Note: The function key F6 "DR Source" /Direct Reader Source) allows you to choose the
source of light for the polychromator. The possible choices include, Sample Source, FET's,
Fatigue Lamp, and None. Please ensure that Sample Source is chosen (as a default). If any
other source, no light from the torch will be measured.
6.5.6. To exit from the plasma control panel, press "Esc" and you will return to the ThermoSpec
Main Menu.
6.5.7. Ensure that the Ar gas flow for purge of POP is set at 8 L/min (gas meter is located on the
front panel just below the POP).
6.5.7. The thermal equilibration period: Allow the instrument to warm-up for 60 minutes before
taking quantitative analytical data, such as standardizing or analyzing unknowing samples.
However, because the spectrometer is fully operational, you can immediately begin to take
qualitative data, such as spectral scans.
Peristaltic Pump Optimization.
The peristaltic pump is equipped with a pressure platen cartridge which holds the pump tubing
and presses the tubing against the rollers. For proper operation, and to extend the life of the
pump windings, the pressure on the pump tubing needs to be properly adjusted. The pressure is
adjusted using the pressure control level on top of the pump tubing cartridge.
6.6.1. Use the following procedure to adjust the pressure on the Sample and Rinse Water Pump
Tubing-.
6.6.1.1. Adjust the pump speed to zero.
6.6.1.2. Adjust the pressure control lever so that the minimum pressure is applied
to the pump.
6.6.1.3. Remove the sample introduction tube from the rinse, and return it after a
second.
6.6.1.4. Observe the air bubble moving through the tubing.
6.6.1.5. Increase the pressure to the point where the air bubble comes to a
complete stop. The pressure is now set correctly.
6.6.1.6. Return the pump to its normal speed, and make sure the bubble moves
smoothly through the tubing.
6.6.2. Set the pressure control lever of the Internal Standard Pump Tubing on two clicks less than
the pressure control lever was previously on the sample pump tubing (steps 6.5.1.1. -
6.5.1.5).
Autosampler Table Set-up - While the instrument is warming up, archive the data from the
previous run and print a summary report; then delete/destroy the previous run-data, (refer to
Section 7. DATA ARCHIVAL) . A new autosampler table must to be edited for a new analytical
run. The new autosampler table can be created as follows:
6.7.1. From the Main Menu select the FILER option from the IMS module.
6.7.2. Select option 5 for Autosampler Tables.
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6.10.2. From the Main Menu under SETUP select PROFILE. (Note: Also entry points for Profile
are available from ANALYSIS, CALIBRATION, and polychromator WAVELENGTH
TIME SCANS)
6.10.3. Calibrate the potentiometer (or vernier). Note: This procedure is done when the
instrument is new, and if the tank atmosphere has been changed (as from argon/nitrogen
to air).
6.10.3.1. After ensuring that As Standard has reached the plasma, select F3
"Automatic"and then F1 "Run".
6.10.3.2. If the resulting profile does not show a peak position of between +/- 0.5,
move the vernier (located on the front panel of the polychromator) 100
units in either direction, press the "Esc" key and repeat the Automatic
(Interactive) profile.
6.10.3.3. Press F5 "Calc K" and follow the instructions of entering vernier positions
and pressing the "Enter" key. The computer will then calibrate the vernier
with respect to peak offset.
6.10.3.4. Press F9 "Done" "when finished.
6.10.4. Adjusting the profile is done in the following manner.
6.10.4.1. Repeat steep 6.8.3.1.
6.10.4.2. A graph of the intensity vs. the spectral shifter position is displayed after
the automatic profile. If the profile is not within +/- 0.2 units of 0 (zero) as
stated by the peak position line, the profile should be adjusted.
6.10.4.3. Press the F1 "Calc SS" key.
6.10.4.4. Enter the appropriate vernier position at the prompt, press "Enter" and
read out the new vernier position from the screen.
6.10.4.5. Adjust the vernier to this new position and the profile is complete.
6.10.4.6. Press the F9 key "Done".
6.10.4.7. Repeat the procedure to insure that the profile is within 0.2 units of 0.
6.10.4.8. Note: If "Calc SS' does not routinely bring the peak to within 0.2 units of
0, then the "Calc K" may need to be repeated.
6.10.1.8. Press the "Esc" key
6.10.1.9. In the Main Menu select ANALYSIS and "Enter". At the Command
prompt, type ra to move the probe to the rinse station.
Note: The Non-Interactive Automatic Profile js only capable to maintain profile to within
0.5 units. If the atmosphere and the climate are such that daily changes are extreme, it is
advisable to use Non-Interactive Automatic Profile every few hours. This profile is
performed the same way as the Interactive Profile, but without using "Calc K" or "Calc SS".
Simply press F9 "Done/Keep" following the scan. The spectrum shifter offset position
displayed with the scan will be used for future analysis. This procedure can be used with
the Autosampler Table by inserting a Profile, (see 6.5.7.)
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MT-046-1
procedure turns off the plasma discharge but leaves the RF generator on, and it will speed up the
subsequent torch ignition and reduce warm up time.
7.2. Automatic shutdown of the instrument.
Before the start of the analytical run perform the following:
7.2.1. Repeat steps 6.8.3.1 - 6.8.3.4.
7.2.2. Press F7 "TermAction" and select action "Shutdown".
Note: For StartUp and Shutdown to full off condition refer to the ICAP 61E Trace Analyzer
Operator's Manual.
8. RESETTING
Occasionally ThermoSpec software on the host computer may lose communication with the
spectrometer controller board, as indicated by an error message on the video display. If this will occur,
you should perform the following steps:
8.1. Exit from the ThermoSpec software by selecting "EXIT" from the Main Menu and entering "Exit
DOS".
8.2. Turn off and on the ON/OFF toggle switch on the computer and load the ThermoSpec software
by typing / in the directory of C:\station\run\bin followed by Enter.
8.3. Turn off and on the ON/OFF toggle switch on the Autosampler.
8.4. If this procedure fails properly reestablish communications, you should shutdown the plasma.
From the Main Menu under "Setup" select "Control Panel," and press the function key F7
"Shutdown.
8.5. Press the Reset button on the front of the optics module.
8.6. Repeat steps 8.1-8.3.
8.7. Reignite the plasma by performing procedures described in 6.5.1.-6.5.6.
9. PRINTING AND ARCHIVAL OF RESULTS
9.1. Printing Raw Data. The raw data consists of the individual replicate data for each sample
analyzed. This raw data must be printed for all samples, QC samples and calibration solutions
analyzed. Use either method 9.1.1 or 9.1.2 to print the raw data:
9.1.1. It is desirable to print raw data to ICP's printer after each sample is analyzed (if a printer
and analyst are available in the lab). In order to print raw data during an analytical run,
the following steps should be perform before an analytical run:
9.1.1.1. In the Main Menu of ThermoSpec Version 6.10 software, select the
CONFIGURA TION option under the SET UP menu.
9.1.1.2. Choose the IDT option that appears to edit the Instrument Default Table.
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MT-046-1
9.2.3.1. Enter the Start & the End of the date and time for the report.
9.2.3.2. Change Sample Type by moving to that field and pressing Spacebar, select
All Types and press Enter.
9.2.3.3. Press F9 (Continue) .
9.2.3.4. Next page will be Editing Report Parameters which allows you to define the
report format. Change the sort method (1st setting) so it reads
'Chronological'. Press F9 to print the report.
9.3. Data Archival. At the end of an analytical run, archive the raw data to a floppy disk used for
archiving the ICP-AES Trace Analyzer instrument files.
9.3.1. Select the IMS (see 7.2.2) module of the ThermoSpec software from the Main Menu, and
choose the FILER option. The FILER allows you to perform file management operations.
These include deleting and changing the names of files, copying files to a floppy disk, etc.
9.3.2. Select option #12 - Samples Archival. Samples Archival allows you to archive, restore,
delete, undelete, or destroy analytical results stored in the instrument operating computer.
9.3.3. Press F1 (ARCHIVE) to display the Selecting Archive Contents screen. This screen allows
you to select which analytical data will be included in the report by entering criteria in
the available fields. An asterisk (*) in any of these fields acts as a wildcard character and
selects all samples in the report. The Date Range is the only screening criteria generally
needed to select the desired data.
9.3.4. Press F1 to set the new path (location to archive the data file) .
9.3.5. Copies are first made to the computer's Hard Drive and then copies onto a floppy in case
of a damaged floppy and unrecoverable data. The Hard Drive copies are then purged
periodically.
9.3.6. Type-C:\archive\YYMMDD.TRP, where YYMMDD.TRP is the name of the file composed
of the date the results were analyzed and an extension designating the instrument (for
example: C:\archive\960308.TRP) , and press Enter.
9.3.7. Enter the start & end dates (including times) that include all of the desired results of the
analytical run.
9.3.8. Press F9 to begin to archive the desired report to Hard Drive.
9.3.9. Press Enter to continue.
9.3.10. Press F9 to finish the archival.
9.3.11. When archiving of the raw data is complete, press Esc to exit from the IMS module.
9.3.12. Exit to DOS and type the following to copy the archived data from the Hard Drive to the
floppy: COPYC:\ARCHIVE\YYMMDD. TRPA:
9.4. Converting Data File. The archived file on the floppy disk needs to be converted and loaded in
the QC-calculator following instructions of the SOP Version 2 of Quality Control Calculator
Program in order to insure archiving was completed successfully.
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MT-046-1
10.2.1. The TYPE column is used to define sample type. Use the following guidelines to set the
TYPE if necessary:
10.2.1.1. SAMP - Type used for ordinary samples. Assign this type to all samples that
do not fit in another category.
10.2.1.2. SRM - Assign this type to all Standard Reference Materials, CCV's, and
PQL solutions.
10.2.1.3. REPL - Assign this type to duplicate and replicate samples.
10.2.1.4. SPK - Assign this type to spiked samples.
10.2.1.5. MDL - Assign this type to all reagent digestion and instrument blank
samples.
10.2.1.6. NONE - Assign this type to all samples where calculations are not desired
or meaningful (blank subtraction, nitric rinse, and samples where
systematic errors occurred such as the autosampler probe missed the
sample tube) .
10.2.2. The DILUTION FACTOR column should contain the dilution factors used by the
instrument. Correct the DILUTION FACTOR when necessary.
10.3. Make Appropriate Selections for SPIKE CODES, SPIKE FACTORS. LIMS TESTS, MATRIX,
BATCH ID: WEIGHT FACTORS and PREPARATION VOLUME prefer to SOP version 2 of
Quality Control Calculator Program) .
10.3.1. LIMS test ID and matrixes. Edit the LIMS Test ID for the samples to match the test
requested (generally W-ICP-TR) , then enter the Matrix when prompted. The W-FRH-
FLT matrix set as a default to all instrument QC samples by QC-calculator program.
10.3.2. Make batch assignments. A batch is a group of samples including precision and spike
recovery samples and all of the samples associated with these, i.e., prepared together
following the same method. At least one batch in a digestion set (group of samples
prepared together) must have a blank and a PQL sample associated with it. Highlight the
samples belonging to a digestion batch including the batch QC. Click the header box on
the BATCH column to assign a batch ID to that batch. Repeat for the remaining batches.
10.3.3. Spike code. Assign the appropriate spike code for the spikes by highlighting all spikes
that used a common spike stock solution and clicking on the Spike Code header box and
choosing the correct code.
10.3.4. Spike factor. Assign spike factors to spiked samples to reflect the amount of spike added
to the sample. For instance, a normal spike would have a spike factor of '1', a double
spike a spike factor of £2' (double amount of spike was added) , etc.
10.3.5. Enter the WEIGHT factors when necessary:
10.3.5.1. Wet weight is used for samples done by waste-ICP and tissue-ICP.
10.3.5.2. Dry weight is used for sample done by S-ICP.
10.4. Results Calculation.
10.4.1. Before calculation, select Save As from the Files menu . Save the file as a .REV file using
the same name as the .RAW file. Click OK to save the file. Perform QC-calculations by
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10.5.5. The results of blanks and PQL's are recorded and the statistical calculations are performed
electronically to establish or update the MDL and PQL for each analyte and matrix based
on every 20 data points.
10.5.6. Examine the data of blanks and PQL's. The QC code 'P/F' will indicate whether the
result of blank or PQL is in or out of control limits. If contamination is found in
instrument blanks and PQL's, the affected samples should be rerun if the sample
concentration for the contaminated analyte is both above the detection limit AND less
than 10 times of the contamination level. If contamination is found in digestion blanks
and PQL's, the affected samples should be redigested if the sample concentration for the
contaminated analyte is both above the detection limit AND less than 10 times of the
contamination level.. Report persistent or unusual contamination of digested samples to
the Metals Group Supervisor and the Inorganic Prep. Group Supervisor so corrective
action can be taken. If contamination is found after 2nd digestion, results may be qualified
and reported according to supervisor's instruction.
10.5.7. Recovery and precision. Samples are spiked (fortified) with known quantities (at least
twice the PQL) of analyte, the recovery is the indication of the accuracy of the analytical
result. The result of RPD (relative percent difference) from duplicate samples is the
indication of precision. The spike and duplicates can be performed at samples preparation
(digestion, extraction) or at instrument according to analytical methods (see 5.) .
10.5.8. Examine the recovery and precision data to ensure that they are within control limits for
the requested analytes. A letter appears in the Pass/Fail column of the component
table/baby table of the .REV file. A 'P' indicates the adjacent value passes, an 'F'
indicates failure, and a 'Q' indicates a warning value that passes marginally. Examine
precision data from duplicate sample if the concentration of analyte is over PQL or from
duplicate spike if the concentration is below PQL. If the recovery or precision code is 'F',
the affected samples have to be rerun or redigestion, dilution or alternate digestion
methods may be used. Results may be qualified at the 2nd failure according to supervisor's
instruction.
10.5.9. Examine the recovery of CCV's. If the recovery code of CCV is 'F', all samples followed
it or before it must be rerun.
10.5.10. Completing initial review. Select component results for reporting, or upload as per QC
Plan (change Y/N flags) :
10.5.8.1. Highlight a group of samples that share a common set of analytes desired
for upload.
10.5.8.2. Select the Change Upload Status by Component option from the Options
menu.
10.5.8.3. Highlight the desired analytes, and click OK. Repeat this step until all
desired analyte rows have a lY' Upload Status.
10.5.8.4. Add appropriate comments when necessary.
10.5.8.5. Attach the component backlog for the samples analyzed to the raw data
printout from the instrument.
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MT-046-1
hood in the metals lab. These wastes should be dumped in the appropriate waste storage container
found in the Hazardous Waste storage room in Bldg. C.
11.4. All the non-hazardous waste water can be dumped into sink if its pH range is 5 - 10. If it is not,
the waste water has to be neutralized before dumping.
12. REFERENCES
12.1. EPA Method 200.7
12.2. EPA Method 6010A
12.3. TJA ICAP 61E Trace Analyzer Operator's Manual
12.4. Metals Waters and Sediments Digestion SOP
12.5. Comprehensive Quality Assurance Plan, Chemistry Section, Bureau of Labs, DEP, April 1998
12.6. Laboratory Safety SOP Manual
12.7. Contingency Plans and Emergency Procedures for a Hazardous Waste Generator
12.8. QC Calculator SOP
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Revision date: 4/16/98
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MT-046-1
Appendix A
Stock Standards
ELEMENT
STOCK SOLUTION
CATALOG #
A1
Spex 10,000 ppm
PLAL2-3X
A1
Inorganic Ventures 10,000 ppm
Sb
Spex 1,000 ppm
PLSB7-2Y
Sb
CPI 1,000 ppm
S4400-10023
As
Spex 1,000 ppm
PLAS2-2Y
As
Inorganic Ventures 1,000 ppm
Ba
Spex 1,000 ppm
PLBA2-2Y
Ba
CPI 1,000 ppm
S4400-100041
Be
Spex 1,000 ppm
PLBE2-2Y
Be
Inorganic Ventures 1,000 ppm
Cd
Spex 1,000 ppm
PLCD2-2Y
Cd
Inorganic Ventures 1,000 ppm
Ca
Spex 10,000 ppm
PLCA2-3X
Ca
CPI, 10,000 ppm
4400-10M91
Cr
Spex 1,000 ppm
PLCR2-2Y
Cr
Inorganic Ventures 1,000 ppm
Co
Spex 1,000 ppm
PLC02-2Y
Co
CPI 1,000 ppm
4400-1000131
Cu
Spex 1,000 ppm
PLCU2-2Y
Cu
Inorganic ventures 1,000 ppm
Fe
Spex 10,000 ppm
PLFE2-2X
Fe
CPI, 10,000 ppm
4400-10M261
Pb
Spex 1,000 ppm
PLPB2-2Y
Pb
Inorganic Ventures 1,005 ppm
Ms
Spex 10,000 ppm
PLMG2-3X
Mr
CPI, 10,000 ppm
4400-10M311
Mn
Spex 1,000 ppm
PLMN2-2Y
Mn
Inorganic Ventures 10,029 ppm
Ni
Spex 1,000 ppm
PLNI2-2Y
Ni
Inorganic Ventures 1,000 ppm
K
Spex 10,000 ppm
PLK2-3X
K
Inorganic Ventures 10,000 ppm
Se
Spex 1,000 ppm
PLSE2-2Y
Se
CPI 1,000 ppm
S4400-1000491
Ag
Spex 1,000 ppm
PLAG2-2Y
Ag
High Purity Standards
100051-1
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Appendix B
Spike Solutions
M
Water Spike
(HI1+2+AG)
Sediment
Spike
(UNIVSED)
Instrument
Mineral Spike
(MIN)
Mineral Spike
(MIN-LOW)
Mineral Spike
(MIN; SF = 5)
A1
200*
20 ppm
2.0 ppm
100 ppm
As
100
400
Sb
100
400
Ba
400
1000
Be
20
50
B
200
Cd
20
100
Ca
20 ppm
2.0 ppm
100 ppm
Cr
100
400
Co
50
200
Cu
100
200
Fe
200*
20 ppm
2.0 ppm
100 ppm
Pb
100
400
Mp
20 ppm
2.0 ppm
100 ppm
Mn
100
400
Mo
50
200
Ni
100
200
K
20 ppm
2.0 ppm
100 ppm
Se
200
400
a£
30
Na
20 ppm
2.0 ppm
100 ppm
Sr
2000
1000
T1
200
400
Sn
200
400
Ti
50
200
V
50
200
Zn
100
400
* low water spike
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Revision Date: 04/21/98 by T.M. Chandrasekhar
Authors: F.Booeshahgi, M.Witt, K. Cano
MT-01I-2
ANALYSIS OF TOTAL MERCURY IN WATER BY COLD VAPOR
ATOMIC ABSORPTION
1. SCOPE AND APPLICATION
1.1. This method details the analysis of water samples for total mercury content utilizing cold
vapor-atomic absorption spectroscopic techniques. It is applicable to the determination
of mercury in surface, saline effluent, and waste waters.
2. SUMMARY OF THE MEHOD
2.1 After digestion, which converts all mercury to Hg +2, samples are treated with
hydroxylamine hydrochloride solution to remove excess oxidizing reagents.
2.2 Each sample digestate is introduced into a reducing cell via an autosampler/peristaltic
pump delivery system. In the delivery system, the mercuric ions are reduced to mercury
vapor with a stannous chloride solution and purged into an absorption cell with Argon
gas. The mercury present is measured as a change in absorption in a photomultiplier
tube.
3. APPARATUS AND EQUIPMENT
3.1 Varian SPECTRAA-400 with a Mercury hollow cathode lamp.
3.2 VGA-76/ 77 reagent pumping unit.
3.3 Black-Purple sample pump tube for the VGA-76/ 77 pump (1 needed).
3.4 Black-Black reagent pump tube for the VGA-76/ 77 pump (1 needed).
3.5 Varian gas-liquid separator.
3.6 Varian Cold Vapor absorption cell.
3.7 SPS-5 Sample Preparation System.
4. REAGENTS AND CHEMICALS
4.1 1.5 N Sulfuric Acid: Add 10.5 ml optima grade sulfuric acid to a 250 ml volumetric flask
filled half full with DI water. Dilute to volume and mix well. Prepare fresh weekly.
4.2 12% Hydroxylamine Hydrochloride Solution: Add 60 grams of hydroxylamine
hydrochloride to a 500 ml Nalgene bottle. Dilute to volume with DI water. Mix well.
4.3 10% Stannous Chloride Solution: Fill a 500 mL Nalgene bottle half full with DI water.
Slowly add with mixing 26 ml of optima grade sulfuric acid and mix gently (work in a
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5.2.4. Add 5 mis 5% potassium permanganate to all standard vessels. Add 4 mis 5%
potassium persulfate to all standard vessels. Tighten cap and invert standard
vessels to mix. Loosen caps and allow to cool.
6. SAMPLE ANALYSIS/QUANTITATION
6.1 Turn on power switches for VarianAA, Varian computer, printer, and
autosampler. Turn on the Argon pressure from the cylinder or house line. Set
the second stage regulator to 50 psi. Varian recommends a pressure range of
42-58 psi.
6.2 At the SpectrAA main menu, select SpectrAA Analysis (1), then select SpectrAA Flame
SPS (1), then push the index (F10) key on the computer keyboard and select sequence
selection, menu item 10. Push the clear sequence (Fl) and select the appropriate method
number and then press the index (F10) key. The instrument should load the correct
program and select the correct lamp.
6.3 Record the date, approximate time and lamp element (Hg in this case) in the lamp time
logbook or equivalent. During the instrument setup, allow the VarianAA to warm up for
at least 1 hour.
6.4 Select instrument parameters, menu item 4. Check that the instrument
parameters are as follows:
Lamp Position 3 (dependent upon instrument)
Lamp Current 4 (suggested by manufacturer)
Slit Width 0.5
Slit Height Normal
Wavelength 253.7 nm
Flame Air Only
Sample Introduction Auto Normal
Replicates 3
Measurement Time 5.0 sec
Delay Time 75 (dependent upon instrument)
Background On
6.5 Select report format (13) from the main menu and enter your name for Operator, the
date of analysis (today's date) and indicate in the batch name that it is a Hs Water
analysis followed by the date. This information is important because it is used as a label
when archiving the data to disk.
6.6 Select sample labels (F6) or select it from the index menu. Using the barcode labels
printed on the sample bottles, scan in the sample labels just as they are to be organized on
the autosampler rack. The scanner is located on the side of the PC, near the keyboard.
Barcodes for blank, W-STD3, etc. can be scanned from the barcode master table located
near the instrument. DO NOT include the calibration standards; start from the first
SAMPLE.
(Use the scanner instead of hand typing whenever possible. It reduces typing errors and
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6.11. Make sure that the argon pressure has been turned on and is reading 50 psi. DO NOT
attempt to run the VGA-76/ 77 pump without argon flow! Allow system to run for 10-15
minutes to stabilize the argon pressure. After 10-15 minutes, check the pressure again
and adjust to 50 psi if necessary. Check occasionally during the run, but do not adjust
during the run. Flow adjustments during the run will affect the instrument calibration.
6.12 Begin tightening the sample friction screw until there is smooth flow through the sample
line (use deionized water as your test solution). Then tighten the screw approximately 1/2
turn more. The flow is now at maximum flow rate. ADDITIONAL tightening will
DECREASE the flow rate. Repeat this process for the reagent line.
6.13 Place the reagent line (Black, Black tubing) into the stannous chloride solution bottle. To
place the sample needle into rinse station go to index. Select Sample Changer (8) and
push probe down key (F2). Allow system to run 10-15 minutes before starting.
6.14 Prepare all sample for analysis by adding 2.0 ml of hydroxylamine hydrochloride
solution. Tighten the caps and gently invert tubes two times to mix. Loosen the cap to
release pressure and place in sonicator bath for 2-4 minutes to help break up any
particles. MAKE SURE to mix all visible sediments into the liquids in the tubes.
6.15 If a purple color persists, add additional hydroxylamine hydrochloride solution in 1.0 ml
increments and mix until the solution is colorless. RECORD HOW MUCH
ADDITIONAL hydroxylamine hydrochloride was added. It will be needed later to
correct for volume changes.
6.16 Transfer samples, standards and QC into clean, disposable 30 ml culture tubes.
6.17 Place standards in Sample Rack #2 in positions 1-4. The rezero blank ALWAYS goes in
position number 6.
6.18 Go to the index menu (F10) and select optimization (6) from the menu. The screen now
displays the lamp alignment and energy outputs from the system. Tilt the sample cell out
of the path of the light beam. Make sure light path is clear of obstructions. The Hg lamp
adjustment knobs are at the left of the machine (base of the lamp). Turn these knobs to
maximize the bar graph signal (biggest bar length you can get). Press the rescale (Fl)
several times during this optimization procedure to update the photomultiplier voltage.
When satisfied with the adjustments, RECORD the photomultiplier voltage in the
"without cell" column in the lamp logbook. This number is the direct lamp output value
without the sample cell. Recording it regularly will allow the analysts to track the lamp's
performance.
6.19 Flip the clean sample cell into the path of the light beam. By using the same optimization
screen used in step 6.18, optimize the Hg output by adjusting the sample cell position
(biggest bar length). Use the horizontal and vertical adjustment knobs as well as the xy
plane lever, all of which are located near the sample cell. DO NOT adjust the lamp at this
point. Record the voltage in the "with cell" column. (Compare with numbers in the log
book.)
6.20 Attach the entire VGA-76 or equivalent pumping unit to the front of the VarianAA
instrument. Attach the sample cell entry line to the top of the gas-liquid separator. Let
the entire system pump for approximately 10-20 minutes.
6.21 Select the signal graphics (18) from the index menu to check the instrument baseline.
-------
7.5 Select advanced report format (F2), and use the following settings:
report output: print
page length : 66 ; if using orator font, page length = 63.
Line up the printer paper to the top of a new page and press the print report (F6).
7.6 In order to upload data into the QC calculator, you must create a .DIF formatted file. To
create, a .DIF file, go to report manager (1), select current results or data set number to
be printed and press enter. Select element number and press (F2). The parameters are
the same as for the printed report.
7.7. Press (F2) to go to advanced report format, At the advanced report format option
select.report output = create .DIF File (use Home key) and enter date type 8 digit name
for the file followed by .dif (ex: use 940802FT.DIF to indicate that the analysis date was
940802 and the tissue type was Fish Tissue). Select print report and the .DIF will be
created on the PC hard drive (c:\varian\reportsy?/e/iawie.DIF)
8 QUALITY CONTROL
WATER
CALIBRATION CURVE
R £ 0 999
MDL
0 100 ug/L
Dl BLANKS
-0 001 < MEAN ABSORBANCE <0 001
LEVEL
RECOVERY
Rl'D
PQL
0.200 ug/L
70% - 130%
NIST 1641C
2 50 ug/L
85%- 115%
DUP SAMPLE
< 20%
DUP. SPIKE
0.400 ug/L
75% - 125%
< 20%
CCV
any
85%- 115%
9. SAFETY/HAZARDOUS WASTE MANAGEMENT
See SOP MT-012-2, "Mercury Waste Disposal", for correct waste disposal procedures.
10. REFERENCES
10.1. Varian SpectrAA 40/400 series instrument owner's manual
10.2. Varian SPS5 autodilutor/autosampler owner's manual
10.3. Varian VGA 76/77 owner's manual
10.4. EPA Method 245.1. "Methods for the Determination of Metals in Environmental
-------
Revision Date: 04/21/98 by T.M. Chandrasekhar
Authors: F.Booeshahgi, M.Witt, K. Cano. 7/'//(/ 5?
MT-008-2 /ft*-'
-------
5.2.4.
Add 10 mis of 5% potassium permanganate to all standard vessels. Add 4 mis
of 5% potassium persulfate to all standard vessels. Tighten cap and invert
standard vessels to mix. Loosen caps and allow to cool.
6. SAMPLE ANALYSIS/QUANTITATION
6.1 Turn on power switches for VarianAA, Varian computer, printer, and
autosampler. Turn on the Argon pressure from the cylinder or house line. Set
the second stage regulator to 50 psi. Varian recommends a pressure range of
42-58 psi.
6.2 At the SpectrAA main menu, select SpectrAA Analysis (1), then select SpectrAA Flame
SPS (1), then push the index (F10) key on the computer keyboard and select sequence
selection, menu item 10. Push the clear sequence (Fl) and select the appropriate method
number and then press the index (F10) key. The instrument should load the correct
program and select the correct lamp.
6.3 Record the date, approximate time and lamp element (Hg in this case) in the lamp time
logbook or equivalent. During the instrument setup, allow the VarianAA to warm up for
at least 1 hour.
6.4 Select instrument parameters, menu item 4. Check that the instrument
parameters are as follows:
Lamp Position
3 (Dependent upon
instrument)
Lamp Current
4 (Suggested by
manufacturer)
Slit Width
0.5
Slit Height
Normal
Wavelength
253.7 nm
Flame
Air Only
Sample Introduction
Auto Normal
Replicates
3
Measurement Time
5.0 sec
Delay Time
75 (Dependent upon
instrument)
Background
On
6.5 Select report format (13) from the main menu and enter your name for Operator, the
date of analysis (today's date) and indicate in the batch name that it is a Hg Sediment
analysis followed by the date. This information is important because it is used as a label
when archiving the data to disk.
6.6 Select sample labels (F6) or select it from the index menu. Using the barcode labels
printed on the sample bottles, scan in the sample labels just as they are to be organized on
the autosampler rack. The scanner is located on the side of the PC, near the keyboard.
Barcodes for blank, W-STD3, etc. can be scanned from the barcode master table located
near the instrument. DO NOT include the calibration standards; start from the first
SAMPLE.
(Use the scanner instead of hand typing whenever possible. It reduces typing errors and
-------
6.11 Make sure that the argon pressure has been turned on and is reading 50 psi. DO NOT
attempt to run the VGA-76/ 77 pump without argon flow! Allow system to run for 10-15
minutes to stabilize the argon pressure. After 10-15 minutes, check the pressure again
and adjust to 50 psi if necessary. Check occasionally during the run, but do not adjust
during the run. Flow adjustments during the run will affect the instrument calibration.
6.12 Begin tightening the sample friction screw until there is smooth flow through the sample
line (use deionized water as your test solution). Then tighten the screw approximately 1/2
turn more. The flow is now at maximum flow rate. ADDITIONAL tightening will
DECREASE the flow rate. Repeat this process for the reagent line.
6.13 Place the reagent line (Black, Black tubing) into the stannous chloride solution bottle. To
place the sample needle into rinse station go to index. Select Sample Changer (8) and
push probe down key (F2). Allow system to run 10-15 minutes before starting.
6.14 Prepare all sample for analysis by adding 4.0 ml of hydroxylamine hydrochloride
solution. Tighten the Nalgene caps and gently invert bottles two times to mix. Loosen the
cap to release pressure. MAKE SURE to mix all visible sediments into the liquids. Filter
any samples that contain particles which will not dissolve with a 10 ml syringe and a .45
PP filter.
6.15 If a purple color persists, add additional hydroxylamine hydrochloride solution in 1.0 ml
increments and mix until the solution is colorless. RECORD HOW MUCH
ADDITIONAL hydroxylamine hydrochloride was added. It will be needed later to
correct for volume changes.
6.16 Transfer samples, standards and QA into clean, disposable 30 ml culture tubes.
6.17 Place standards in Sample Rack #2 in positions 1 -4. The rezero blank ALWAYS goes in
position number 6.
6.18 Go to the index menu (F10) and select optimization (6) from the menu. The screen now
displays the lamp alignment and energy outputs from the system. Tilt the sample cell out
of the path of the light beam. Make sure light path is clear of obstructions. The Hg lamp
adjustment knobs are at the left of the machine (base of the lamp). Turn these knobs to
maximize the bar graph signal (biggest bar length you can get). Press the rescale (Fl)
several times during this optimization procedure to update the photomultiplier voltage.
When satisfied with the adjustments, RECORD the photomultiplier voltage in the
"without cell" column in the lamp logbook. This number is the direct lamp output value
without the sample cell. Recording it regularly will allow the analysts to track the lamp's
performance.
6.19 Flip the clean-sample cell into the-path of the light beam. By using the same optimization
screen used in step 6.18, optimize the Hg output by adjusting the sample cell position
(biggest bar length). Use the horizontal and vertical adjustment knobs as well as the xy
plane lever, all of which are located near the sample cell. DO NOT adjust the lamp at this
point. Record the voltage in the "with cell" column. (Compare with numbers in the log
book.)
6.20 Attach the entire VGA-76 pumping unit to the front of the VarianAA instrument. Attach
the sample cell entry line to the top of the gas-liquid separator. Let the entire system
-------
calibration graph : NO.
volume correction : YES to implement dilution factors from 7.2
NO for all other cases.
7.5 Select advanced report format (F2), and use the following settings:
report output: print
page length : 66 ; if using orator font, page length = 63.
Line up the printer paper to the top of a new page and press the print report (F6).
7.6 In order to upload data into the QC calculator, you must create a .DIF formatted file. To
create a .DIF file, go to report manager (1), select current results or data set number to
be printed and press enter. Select element number and press (F2). The parameters are
the same as for the printed report.
7.7 Press (F2) to go to advanced report format, At the advanced report format option
select.report output = create .DIF File (use Home key) and enter date type 8 digit name
for the file followed by .dif (ex: use 940802FT.DIF to indicate that the analysis date was
940802 and the tissue type was Fish Tissue). Select print report and the .DIF will be
created on the PC hard drive (c:\varian\reportsy?/e/io/;ie DIF)
8 QUALITY CONTROL
SEDIMENT
CALIBRATION CURVE
R > 0 999
MDL
0.125 ug/L*
Dl BLANKS
-0 001 < MEAN ABSORBANCE ^ 0.001
LEVEL
RECOVERY
Kl'D
PQL
0 25 ug/L *
70% - 130%
MESS-2
0.092 mg/Kg
85% - 115%
DUP. SAMPLE
< 20%
DUP. SPIKE
1.25 ug/L *
75% - 125%
< 20%
CCV
any
85%- 115%
*Based on lg dry wt in 40mls water
9. SAFETY/HAZARDOUS WASTE MANAGEMENT
-------
Revision Date: 11-4-96/8-26-96/5-5-98
Author(s): Raul A. Ramirez, Colin Wright
NU-032-2
Determination of Low Level Cyanide in Water using the Lachat Autoanalyzer
1. SCOPE AND APPLICATION
This method is applicable to the determination of cyanide in drinking, surface and saline
waters, domestic and industrial wastes. The applicable range for this method is
0.010 mgCN/L to 0.50 mg CN/L.
2. SUMMARY OF THE METHOD
2.1. This method is based on the Lachat Quickchem Method No. 10-204-00-1-A and
EPA method 335.2. Cyanide as hydrocyanic acid (HCN) is released from
cyanide complexes by means of a reflux-distillation operation and absorbed in a
scrubber containing sodium hydroxide solution (see operation of Midi-Vap
Cyanide Distillation Apparatus for further instructions). Subsequently, total
cyanide from alkaline distillates is converted to cyanogen chloride, CNC1, by
reacting with chloramine T at pH < 8. The CNC1 forms a red blue color by
reacting with pyridine-barbituric acid reagent. The color is read at 570 nm.
Note: Both HCN and CNC1 are highly toxic gases. Proper handling of standards
and waste is important.
2.2. Interferences
2.2.1. Interferences are eliminated or reduced by using the distillation
procedure.
2.2.2. Sulfides adversely affect the colorimetric procedure. Test all
distillates which give a positive result for cyanide for the presence of
sulfide (a drop of the distillate is added to lead acetate paper which
will turn dark on contact with sulfides). If sulfides are present the
analysis is compromised. (Sulfides should be removed in the field
prior to preservation.)
3. APPARATUS AND EQUIPMENT
3.1. Instrumentation - Lachat Quickchem Automated Flow Injection ion Analyzer.
Method name is Cyanide.
3.2. Pump Tubing:
• Carrier is 0.25 M NAOH and the line is yellow-yellow.
-------
Reagents And Chemicals
5.2.1. 0.25 N NaOH
5.2.2. 50%[v/v] H2S04
5.2.3. Dry KCN
Handling and Disposal of Cyanide Standards
NOTE: If KCN comes in contact with acid, hydrogen cyanide, a deadly gas,
is generated. Because of this, it is vital that the following standard
prep instructions be followed closely !! Read this SECTION and the
hazard information on cyanide before preparing or using any
cyanide standards !
5.3.1. When certain forms of cyanide (i.e. potassium cyanide) come into
contact with acid, a deadly gas (HCN) is produced. It's very important
that,cyanide standards be handled correctly. Wear gloves at all times
when handling cyanide standards. Prepare all standards in a hood.
5.3.2. Disposal of Cyanide Standards
5.3.2.1 Standards at 0.2 PPM and above need to be poured into a
cyanide standard waste bottle. Do not dump the standards in
the reagent waste bottle.
5.3.2.2. Standards below 0.2 PPM can be poured down a hood sink.
Be sure to run water prior to and after dumping the standard in
order to flush the trap of any acid residue.
5.3.3 Handling Small Spills and Glassware Rinsing
5.3.3.1. Rinse glassware that contained 1 PPM and higher CN once
with NaOH solution. Dispose of the initial rinse solution in
the CN std. waste bottle. Then rinse glassware in hood sink
several times. Clean glassware with DI water.
5.3.3.2. Rinse glassware that contained less than 1 PPM CN several
times in the hood sink prior to cleaning with DI water.
5.3.3.3 Small spills of CN solutions or large spills of low level
standards should be wiped up using NaOH solution. Place
used paper towels in a plastic bag prior to disposal. For small
spills of dry KCN reagent, carefully collect the reagent and
dispose of it in the CN standard waste bottle (pH of 12). Wipe
-------
5.4.4. Working Standards.
Follow the same precautions when preparing the standard as you did
when preparing the stock standard. Wash 5-100 ml volumetric flasks
(labeled for cyanide) with DI water and 0.25 M NaOH. Add 80 ml of
0.25 M NaOH and then make standards as followed using the 50.0 PPM
working stock cyanide standard.
CN STANDARD 50 PPM STOCK ,
0.500 PPM 1.0 ml
0.200 400 uL
0.100 200
0.050 100
0.020 040
0.000 000
Then dilute all to the mark and store in refrigerator. Standards should be
made every 2 weeks.
5.4.5. Alternative Standard
An alternative standard (ALTQC) is prepared from the 1000 PPM stock
Fisher solution. Prepare a 50 PPM standard (see section 5.4.3.) using
the Fisher standard and use this to prepare a 0.2 PPM standard (see
section 5.4.4.). Prepare every two weeks.
6. SAMPLE ANALYSIS/QUANTITATION
6.1. Print backlog to determine which samples are to be run. Print samples for W-
CN and S-CN. If samples are require CN analysis then inform the prep group
supervisor so that the samples can be distilled. After distillation the samples will
be stored in a refrigerator in the nutrients lab. On the day of analyses remove
samples from refrigerator and let them come to room temperature.
6.2. The standards should be removed from the refrigerator as well as the reagents.
Put them in the hood in order to minimize fumes from the pyridine.
6.3 Please refer to quickchem Method 10-204-00-1-A in the Lachat method manual
located in the nutrients lab. Also refer to the Lachat operation SOP (NU-036-1).
Also sonicate reagents and carrier for at least 30 mins.
6.4. Locate the manifold for CN. Check condition of pump tubing, change if needed.
Check condition of platens. Check condition of tubing on manifold.
NU-032-2.DOC
-------
9.2. The instrument reagent waste may contain excess chloramine T which can react
with cyanide to form toxic CNC1 gas. To reduce this effect bring the waste to
pH of 12 or higher using NaOH solution. Perform this step in the hood. Also,
never dump the cyanide standard waste into the reagent waste bottle.
9.3. When dumping waste in the waste drum be sure to wear a gas mask, gloves,
safety glasses/goggles and lab coat.
10. REFERENCES
10.1. EPA method 335.2 (4-79-020)
10.2. Lachat Quickchem Method 10-204-00-1-A
NU-032-2 DOC
-------
Revision Date: 4-20-98
Author: R.Northup, K. Tate \(Jx'
SV-006-2
Analysis of Base/Neutrals and Acid Extractables by Gas Chromatography/Mass
Spectrometry
1. SCOPE AND APPLICATION
1.1. This method describes the instrumental analysis of base-neutral and acid extractable organics
by GC/MS and is based on the EPA Methods 625 and 8270. The analytes applicable to this
method (as listed in Table 1) may be detected in ground water, surface water, sediments and
wastes by this method. The operating procedures described here are designed to meet or
exceed the requirements for the 625 and 8270 EPA methods.
2. SUMMARY OF THE METHOD
2.1. Sample extracts from the preparation of water, sediment and waste samples by SOP's SV-
001, are analyzed by GC/MS.
2.2. Qualitative identification of the parameters in the extract is performed using the retention
time and the relative abundance of two or three characteristic masses (m/z). Quantitative
analysis is performed using an internal standard technique.
2.3. The following compounds may require special treatment when being determined by this
method.
2.3.1. Benzidine can be subject to oxidative losses during solvent concentration, storage,
and analysis.
2.3.2. Under the alkaline conditions of the extraction step, a-BHC, g-BHC, endosulfan I
and II, and endrin are subject to decomposition. Neutral extraction should be
performed if these compounds are expected.
2.3.3. Hexachlorocyclopentadiene is subject to thermal decomposition in the inlet of the
gas chromatograph, chemical reaction in acetone solution, and photochemical
decomposition.
2.3.4. Pentachlorophenol, 2,4-dinitrophenol, 4-nitrophenol, 2-methyl, 4,6-dinitro-phenol,
and 4-chloro-3-inethylphenol are subject to erratic chromatographic behavior,
especially if the GC system is contaminated with high boiling material.
2.4. Interferences:
2.4.1. Raw GC/MS data from all blanks, samples, and spikes must be evaluated for
interferences. Determine if the source of interference is in the preparation and/or
cleanup of the samples and take corrective action to eliminate the problem.
2.4.2. Contamination by carryover can occur whenever high-level and low-level samples
-------
solvent between samples. In extreme cases, it may be neccessary to analyze a sovent
blank between samples.
3. APPARATUS AND EQUIPMENT
3.1. Bottles--25 mL, amber glass with Teflon-lined screw caps
3.2 Autosampler vials-1.5 mL, with crimp tops with Teflon-lined septa, to fit the Hewlett
Packard 7673 autosampler.
3.3. GC/MS system:
3.3.1. Gas chromatograph, Hewlett Packard 5890 series II or equivalent. Must be
temperature programmable with an injector port designed for splitless injection.
3.3.2. Autosampler, Hewlett Packard 7673 or equivalent, capable of 1 uL injections and
equipped with bottles for solvents to flush syringe between injections.
3.3.3. Mass spectrometer, Hewlett Packard5971, 5972, 5973 or equivalent. Must be
capable of scanning from 35 to 450 amu every 7 s or less, utilizing a 70 V (nominal)
electron energy in the electron impact ionization mode, and producing a mass
spectrum which meets all the criteria in Table 2 when 50 ng of decafluorotriphenyl
phosphine (DFTPP) is injected through the GC inlet.
3.3.4. Data system: A computer system must be interfaced to the mass spectrometer that
allows the continuous acquisition and storage on machine-readable media of all mass
spectra obtained throughout the duration of the chromatographic program. The
computer must have software that allows searching any GC/MS data file for specific
m/z and plotting such m/z abundances versus time or scan number (an Extracted Ion
Current Profile, or EICP). Software must also allow integrating the abundance in
any EICP between specified time or scan number limits. See the Enviroquant
software manual for details.
GC/MS Operating Conditions:
Parameter
Setting
Mass Range:
35-450 amu
Scan Time:
1 scan/sec minimum
GC Oven Temperature Program:
40 °C for 2 min., to 160 °C at 12 C/min., hold at 160 °C for 2
min., 160-300 °C at 8 C/min., hold at 300 °C for 10 min.
Injector Temperature:
260 °C
MS interface temperature:
300 °C
Injection Type:
splitless
Injection Volume:
1 uL
Carrier Gas Flow Rate:
helium at approximately 24 cm/sec linear flow
Purge Off Time
0 min.
Purge On Time
1 min.
3.4 Helium, UPC grade, is the carrier gas in the gas chromatographs. The helium must be
-------
3.5 J&W Scientific DB-5MS capillar)' column (or equivalent), 30M x 0.25 mm x 0.25 urn
REAGENTS AND CHEMICALS
4.1. Standards (see the Standard Preparation SOP SV-009 for preparation instructions)
4.1.1. Calibration Standards 625, 8270 and Chlorinated Pesticide mixes at the following
concentration levels: 4 (or PQL), 8,20, 60, 80, 100 ug/mL. Note: Some analytes
will not be detectable at 4 ug/mL; do not include these when constructing
calibration curves.
NOTE: The 20 ug/mL standards are used as the daily continuing calibration check
standards.
4.1.2. Internal standard solution, 80 ug/mL or 40 ug/ml. This solution is used when any
sample needs dilution and contains the following compounds :
4.1.3. DFTPP (Decafluorotriphenylphosphine) Tuning Standard, 50 ug/mL
4.2. Solvents: HPLC grade Methylene chloride and Methanol, or equivalent grade.
SAMPLE PREPARATION PROCEDURE
See appropriate sample preparation SOPs for water, sediment, waste and TCLP, SOP #s (SV-001-
SV-005).
GC/MS TUNING/CALIBRATION
6.1. Tuning
6.1.1. Tune the GC/MS system prior to the beginning of an analysis run and every 12 hours
thereafter. The tune analysis must meet the criteria in Table 2 for a 50-ng injection
of DFTPP within two scans on either side of the DFTPP apex. Check the scan at the
apex first. If the tune does not pass, then use the autofind DFTPP feature in the
Enviroquant software, which averages 3 scans around the apex. If the tune fails
again, then perform a DFTPP target tune and re-inject the DFTPP standard. Once
the instrument has failed to successfully tune after making several attempts, then it is
time to clean the ion source and perform other preventative maintenance. Other
instrumental problems which can prevent the mass spectrometer from tuning
properly include a contaminated column, a poorly responding EM, or air leaks.
Sample analyses MUST not begin until all the tuning criteria are met.
1,4-dichIorobenzene-d4
naphthalene-d8
acenaphthene-dlO
phenanthrene-dlO
chrysene-dl2
perylene-dl2
6.1.2.
Background subtraction, if needed, should be straightforward and designed only to
-------
6.1.3. Place a hard copy of the DFTPP tuning report(s) in the daily QA/QC folder for the
instrument that was tuned. Include all data in the QA/QC folder, including tune
reports that failed.
6.1.4. Include a DFTPP standard injection at twelve hour intervals during an analysis
sequence and check the tune criteria. If the tune check happens to fail any of the
criteria, then re-analyze all samples that were analyzed after the failed tune check
standard.
6.1.5. The instrument tune must be maintained not only environmental samples, but also
for instrument calibration samples.
6.2. Initial Calibration
6.2.1. Analyze the 625, 8270 and pesticide calibration standards at the following levels:
100, 80, 60,40, 20, 8, and 4 (PQL) ug/mL. At each level, the internal standards
should be present at 40 ug/mL.
6.2.2. For each compound determine the retention time, the primary quantitation ions and
two or three secondary ions to use for qualitative identification. The primary and
secondary ions are already given in the EPA methods 625 and 8270. The major ions
(<10% of the most abundant ion) should be present and the relative intensities of the
major ions should agree within ±20% of the reference mass spectrum.
6.2.3. Tabulate the area of the primary ions against concentration for each compound and
internal standard in the calibration standard mixes. Calculate response factors for
each compound using the equation below.
RF = [AsCjs)
(Ais Cs)
where:
RFj is the average response factor from the initial calibration
As is the area of the m/z for the compound measured
Cis is the m/z for the internal standard
^¦is is the concentration of the internal standard
Cs is the concentration of the compound measured
6.2.4. The initial calibration curve must meet the following criteria:
6.2.4.1. The %RSD of the response factors for each of the target compounds must be
<15%. or the instrument system is considered to be out of calibration.
However, the %RSD must be >30 % for each of the calibration check
compounds. If the %RSD for the compounds are out of these ranges, then
the instrument system must be corrected. Some possible problems include
standard mixture degradation, injection port inlet contamination, and
analytical column contamination and active sites in the column or
chromatographic system.
6.2.4.2. The relative retention times of each compound in each calibration should
-------
6.2.5. Some analytes are very problematic. Benzidine breaks down readily and may not
seen below a 50 ug/mL standard level. Some compounds may not be detected at the
lower standard concentration levels, (i.e., benzidine, 4-nitrophenol). Eliminate these
levels from the analyte's calibration curve. However, the analytes should have a
calibration curve with 5 or more levels. In the case of benzidine, only three levels
may be feasible. The MS may have to be adjusted accordingly (i.e., increase EM
voltage, modify lens settings, etc.) to achieve appropriate sensitivity.
6.2.6. Store all hard copies of the calibration and quantitation reports created in a file
folder and label with the ID file name and calibration file name.
Daily GC/MS Performance and Calibration Check
The initial calibration curve and instrument performance must be verified on each day by the
measurement of one or more check standards.
6.3.1. Analyze 20 ug/mL standards as continuing calibration check standards. These
calibration check standards must be analyzed at the start of each run and at 12 hour
intervals thereafter.
6.3.2. The performance and calibration check standards must meet the following criteria:
6.3.2.1. System Performance Check Compounds (SPCO: The minimum RF of the
SPCC's in Table 1 must > 0.05: If the minimum response factors are not
met, the system must be evaluated, and corrective action must be taken
before sample analysis begins. Some possible problems are standard
mixture degradation, injection port inlet contamination, contamination at the
front end of the analytical column, and active sites in the column or
chromatographic system. This check must be met before analysis begins.
6.3.2.2. Calibration Check Compounds (CCO: After the system performance check
is met, CCCs listed in Table 1 are used to check the validity of the initial
calibration. Calculate the relative percent difference (RPD) using:
RPD = (RFjaviz - RFC)
RFjavg X 100
where:
RFjavg is the average response factor from the initial calibration
RFC is the response factor from current verification check standard
The RPD for all compounds should be less than 30 %. The RPD for any CCC must
be less than 30%. If the percent difference for each CCC is less than 30%, then the
initial calibration is assumed to be valid. If the percent difference is greater than
30% for any one CCC, corrective action must be taken. Problems similar to those
listed for SPCCs could affect this criterion. If no source of the problem can be
determined after corrective action has been taken, a new five-point calibration must
-------
7. GC/MS Sample Analysis
7.1. Each sample extract MUST contain 40 ug/mL of internal standard. Any extract that is dark
in color, suspected of containing petroleum hydrocarbons or high concentrations of any
analytes should be screened on the GC/FID before analyzing on the mass spec. The extracts
should be diluted as deemed necessary. The concentration of internal standard must
remain at 40 ug/mL when diluting samples by adding additional internal standard to
the extract.
7.2. Analyze the extracts by GC/MS by loading the autosampler tray and setting up a run
sequence in the GC/MS software. A vial of DFTPP and the appropriate calibration check
standards (dependent on the customer requested analysis) must be inserted every 12-15
samples to check the tuning and calibration response every 12 hours. If the DFTPP or
calibration check standard fail their criteria, any samples run after them must be reanalyzed
after the criteria have been passed.
7.3. Print a hard copy of the run sequence, date and initial it, and place it in the final data folder.
7.4. Examine the quantitation reports soon after the samples have been analyzed.
7.4.1. Check all of the calibration check standards and DFTPP tune standards analyzed
during the run sequence and insure that they met the minimum criteria given above.
7.4.2. If the response for any of the compounds exceeds the calibration curve, the extract
must be diluted so that the response will be within the limits of the curve, then
reanalyzed. Make sure when performing dilutions to use methylene chloride spiked
with the appropriate levels of internal standard so that their response will be the
same in the dilution as it was in the original extract.
7.4.3. The internal standard responses and retention times in the calibration check standard
must be evaluated immediately after data acquisition. If the retention time for any
internal standard changes by more than 30 sec. from the last check calibration, then
the chromatographic system must be inspected for malfunctions and corrections
must be made. The m/z abundances for all of the internal standards must be within a
factor of two (50% to 200%) from the abundance in the daily calibration standard
check. Corrective action is indicated if the m/z abundance is outside of these limits.
If the holding time for a sample has expired and the internal standard areas are out of
the acceptance range, then the final report must be commented and any positives
detected must be qualified with a "J" to indicate that the result is an estimate.
7.4.4. Surrogate Recoveries. The recoveries must be within the following acceptance
limits:
Compound
Nitrobenzene-d5
2-Fluorobiphenyl
Terphenyl-d]4
Phenol-d5
2-Fluorophenol
2,4,6-Tribromophenol
Surrogate Recovery Acceptance Limits
% Rec. (Water) % Rec. ("Sediment)
35-114
43-116
33-141
10-110
21-110
10-123
23-120
30-115
18-137
24-113
25-121
-------
7.4.5. Check the Matrix Spike and Lab Fortified Blank recoveries. They must be within
the current acceptance ranges. A comment must be added to the final report
explaining any deviation from the routine limits whenever the spikes or surrogates
are out of range.
7.4.6. Check the method blank for any interfering contaminants. The MDLs may have to
be elevated if the blank(s) indicate contamination. The reported MDLs should be at
least 5 times the level detected in the method blank.
Data Interpretation and Quantitation
7.5.1. Two criteria must be satisfied to verify identification of a compound: 1.) elution of
the sample component at the same GC relative retention time as the standard
component: and 2.) correspondence of the sample component and the standard
component mass spectrum. The computer system will check these criteria
automatically (as long as the retention times and mass spectra have been updated
recently with the calibration standard's retention times/spectra) but ALWAYS
manually assess each chromatogram/mass spectrum.
7.5.2. Concentrations (Cs) of each compound and surrogate identified should be calculated
as follows (the computer program will automatically calculate the concentrations for
water samples, including any dilution factors entered; the calculations for sediments
must be adjusted for the weight of the sample and conversion of units to ug/kg):
As is the corrected area of the compound peak
Ijs is the concentration of the appropriate internal standard (in ug/mL)
Vt is the total volume of the extract (usually 1 mL)
DF is the appropriate dilution factor (i.e., 1:10 dilution = a DF of 10)
Ajs is the corrected area of the internal standard
RF is the response factor for the compound being measured
Vh20's *'ie vo'ume of water extracted
Cs = (AsXIisXYtXDF)
(AisXRFXVH2o)
water samples
where:
or
Cs = (AsXIisXYtimD
(Ais)(RF)(Ws)(D)
sediment/waste samples
where:
As, ^is' ^;t' DF, Ajs, and RF= same as for water
Ws = weight of sample extracted or diluted in grams
-------
7.6. TCLP (Toxicity Leaching Characteristic Procedure) Special Reporting/ Calculation
Requirements:
7.6.1. Follow steps in section 7.4.
7.6.2. Unless a sample contains TCLP compounds at or above the Characteristic Levels
listed in following table, it is NOT considered a TCLP exceedance. Some clients
may, however, use different maximum teachability concentrations than those listed
here.
7.6.3. The BNA TCLP analytes (with associated characteristic level) are:
Maximum Concentration of Contaminants for the Toxicity Characteristic (TCLP)
Compound
Characteristic
Compound
Characteristic
Level (ug/L)
Level (ug/L)
o-Cresol
200,000
Hexachlorobutadiene
500
m,p-Cresol (total)
200,000
Lindane (gamma BHC)
400
Cresols (total)
200,000
Nitrobenzene
2000
1,4-Dichlorobenzene
7500
Pentachlorophenol
100,000
2,4-Dinitrotoluene
130
2,4,5-Trichlorophenol
400,000
Endrin
20
2,4,6-T richlorophenol
2000
Hexachlorobenzene
130
7.6.3. If the TCLP extraction resulted in two or more phases which were analyzed separately, the
results from these phases must be mathematically recombined and reported as follows:
Cf = ("Vi x Ci) + ("V? x C?)
V] + V2
where:
Cf = final calculated concentration in ug/mL.
V i = the total volume (mL) of the liquid phase as measured after filtration.
V2 = Total volume (mL) of the extraction fluid used in the tumbling of the
solid phase.
Cj = concentration (in ug/mL) of the analyzed liquid phase sample extract.
C2 = concentration ( in ug/mL) of the analyzed solid phase extract.
HOWEVER: If an analysis of any one of the liquid fractions of the sample indicates that a
TCLP analyte(s) is present in such a high concentration that it exceed the TCLP limit, even
accounting for the dilution from the other fractions, then the sample is considered hazardous
and it is not necessary to analyze the remaining fractions of the sample. It is acceptable to
-------
7.7. For samples containing components not associated with the calibration standards, a library
search is made for the purpose of tentative identification. Guidelines for making tentative
identifications are given in section 8, LIBRARY SEARCH PROTOCOL FOR BNA GC/MS.
7.8. See the BNA QA/QC SOP SV-010 for further details.
8. LIBRARY SEARCH PROTOCOL FOR BNA GC/MS
8.1. If there are any unidentifiable peaks in the chromatogram that are at least 10 % of the nearest
internal standards response (discounting any in-house contaminants in the extraction blank),
conduct a library search. Exceptions to this rule:
8.1.1. If the unknown peaks appear to be part of a petroleum hydrocarbon pattern (like
diesel or kerosene, etc. ), it is unnecessary to search individual peaks, since they are
mostly elements of the petroleum product.
8.1.2. If the peak pattern is a pet. hydrocarbon, identify the petroleum hydrocarbon using
pattern-std. comparison. If the pattern is unrecognizable, report as "unidentifiable
petroleum hydrocarbon pattern ". Estimate the amount of pet. hydrocarbon present
using total ion area calculation of the envelope. Assume the RF is 1. Quantitate as
in step 7.5.2., using Ax as the total petroleum hydrocarbon area. Report result in the
comment section of SMP (using only ONE significant figure) as follows:
Example 1:
Chromatographic pattern similar to diesel, estimated concentration, 3E5 ug/L.
Example 2:
Unidentifiable petroleum hydrocarbon pattern, estimated concentration, 5E6 ug/kg.
8.2. Use the library search program to estimate the concentrations for the unknown peaks. When
reviewing the results from the library search, look at the probability value assigned to the
listed compounds in addition to the mass spectra. Usually, if the search program assigns a
probability of about 60% or greater, it is a pretty good match and the compound may be
reported tentitively.
8.3. If the search program resulted in multiple hits with probabilities of 60% or greater and they
all look like possible matches, then you must attempt to classify the compound. For
example, if you get a 80% match for undecane and a 83% match for dodecane and a 88 %
match for tricosane, and all of the spectra look like plausible matches, report result as
"alkane" and give estimated concentration. If there are a lot of hits for a variety of alkanes,
report as "total alkanes" with the estimated total concentration. This will simplify reporting
if your sample has a lot of unknown alkanes. The same goes for alcohols.
8.4. If the match is below about 60%, or the search program resulted in no matches (i.e.," No
data base entries were retrieved") the spectra will usually suggest a poor match. In this case,
the peak is an "unidentifiable organic compound". You only need to report the total
estimated amount for all unidentifiable organic compounds, not each individual estimated
-------
WARNING: Do not trust any library search program over your own scientific judgment.
Just because the program returns a probability of 35% does not mean that it is
not a match. Look at the spectra; you may have additional information about
the sample that will lead you to a different conclusion than what the search
program concluded. However, it is not necessary to turn each unknown
identification practice into a research project. Exercise caution when utilizing
the search results and do not neglect to examine the returned spectra against
the sample spectra.
8.5. The library search program returns estimated concentration results in ug/mL. You must
apply the correct sample volume or weight extracted to correct the result and calculated the
final estimated result as in step 7.5.2 for water and sediment/waste samples.
8.6. Report final result in the comment section of the final report using the following format (if
sample is a water, use ug/L as units):
Sediment/Waste Example
Comments: Library Search Results (est. conc. in ug/kg)
(2): I. Tentatively Identified Compounds
(3): 4-hydroxy -4-methyI-2-pentanone, 2.5E3; alpha pinene, 1900;
(4): 2-beta-pinene, 510; totaral, 3400; sub.benzenedicarboxylic acid, 340;
(5): total alkanes, 6300.
(6):
(7): II. Unidentifiable Organic Compounds (total): 2.8E4.
9. REPORTING AND DOCUMENTATION
9.1. When analysis is complete, the QC calculator is used to download the final sample results
into the Laboratory Information Management System (LIMS). If a sample has been diluted
or has a dry weight less than 100 %, then make sure that the information was entered
properly into the calculator.
9.2. Add the appropriate qualifiers and comments to the sample data in the calculator after
performing a complete review of the sample data and QC data.
9.3. Definitions of the available qualifing codes are:
A- Value reported is the mean of two or more determinations.
I - Value reported is less than the practical quantitation limit (PQL) and greater than the
minimum detection limit (MDL).
J - Estimated value; use if QC for that compound is out of limits.
K - Actual value is known to be less than value given.
L - Actual value is known to be greater than value given.
N - Presumptive evidence of presence of material.
O - Sampled, but analysis lost or not performed.
Q - Sample held beyond normal holding time.
T- Value reported is less than MDL.
U - Material was analyzed for but not detected. The value reported is less than MDL.
V - Analyte was detected in both sample and method blank.
If value reported is equal to the MDL, report value + I
-------
• If value reported is between the MDL and PQL, report value +1
• Always report 2 significant figures, except for petroleum hydrocarbons, report 1
significant figure:
Examples: 1.456 E +04 = 1.4 E4
1.7563E5 = 1.8 E5
68.4= 68
0.103= 0.1
9.4. All quantitation reports for a single extraction batch should be placed in a folder labeled with
the job number, the sample numbers, and the type of analysis.
9.5. Retrieve the field folders (containing the field sheets) and check the data against the field
sheets to see if it makes sense (i.e., does the trip blank contain several hits while an effluent
sample does not?) If anything looks suspicious, further research is necessary before posting
results.
9.6. Enter the results for each sample in the analysis results form. Put a copy in the analysis and
a copy in the analysis results notebook.
9.7. Enter the QC into the QC program and put a print-out in the field folder and the data folder.
9.8. Submit the project folder and field folder to the BNA section supervisor. The supervisor will
review results and then authorize the test. The supervisor will then return the data folder to
the chemist who files the folder in the BNA GC/MS lab The field folder including the QC
results sheet is submitted to the Evironmental Manager of the organic chemistry section, who
authorizes the job.
10. DATA ARCHIVAL
10.1. For the Enviroquant GC-MS system:
10.1.1. Move the data files soon after collection from the hard disk of the instrument
computers to the network drive TLHCHEM2/BNA. Each GC/MS instrument has its
own designation and also has a corresponding instrument subdirectory for data
storage. The instrument designations and subdirectories are called BNA1, BNA2,
or BNA3.
10.1.2. Once the data has been authorized, the data must be moved again to the
TLHCHEM2/ BNA/ARCHIVE directory. This directory contains the instrument
subdirectories, BNA1, BNA2, and BNA3. The data files moved to this directory are
copied onto an optical disk by the section's system manager once there is sufficient
data to fill a disk.
10.1.3. The achived data may be retieved by making a request to the system manager or the
BNA supervisor. Make sure when setting up an injection sequence to write
down the name of the data files with the associated sample information in the
injection log. This is the only way that data files.may be cross referenced to
their sample ID.
-------
See BNA SOP SV-010 for detailed information
12. DETERMINATION OF METHOD DETECTION LIMITS
12.1. The MDLs were established using procedures given in EPA 40 CFRPart 40, Appendix B.
13. SAFETY/HAZARDOUS WASTE MANAGEMENT
See SOP OG-OOl for specific details on safety and hazardous waste mangement.
14. REFERENCES
14.1. Hewlett Packard HP 59872C GC/LC/MS RTE-A Data System Manual, volumes 1 & 2
14.2. Hewlett Packard Gas Chromatograph and Mass Spectrometer Operating Manuals
14.3. Perkin Elmer GC/FID Operating Manual
14.4. Test Methods for Evaluating Solid Wastes, Third Edition, SW-846, Method 1311 (rev. 7/92)
and Method 1312 (rev. 9/92).
14.5. Code of Federal Regulations, Title 40, Part 136, Vol. 49, No. 209, Method 625:
Base/Neutrals and Acids. 10/26/84.
14.6. Test Methods for Evaluating Solid Wastes, Third Edition, SW-846, Method 8270B. revision
2, 9/94.
-------
TABLE 1: MDLs/PQLs in Water
The listed MDL and PQL values are approximate and may change with time and matrix type.
Analyte
MDL
PQL
Acenaphthene
1.0
4.0
Acenaphthylene
1.0
4.0
Acetophenone
1.0
4.0
Aldrin
1.5
6.0
Anthracene
1.0
4.0
Azobenzene/1,2-DiphenyIhydrazine
1.0
4.0
Benzo[a]anthracene
1.0
4.0
Benzo[b]fluoranthene
1.0
4.0
Benzo[k]fluoranthene
1.0
4.0
Benzo[a]pyrene
1.0
4.0
Benzo[g,h,i]perylene
2.5
10
Benzyl butyl phthalate
5.0
20
alpha-BHC
1.5
6.0
beta-BHC
1.5
6.0
gamma-BHC
1.5
6.0
delta-BHC
1.5
6.0
Benzidine
100
400
Bis(2-chloroethyl)ether
1.0
4.0
Bis(2-chloroethoxy)methane
1.0
4.0
Bis(2-chloroisopropyl)ether
4.5
18
Bis(2-ethylhexyl)phthalate
15
60
4-Bromophenylphenyl ether
1.0
4.0
2-Chloronaphthalene
1.0
4.0
4-Chlorophenylphenyl ether
1.0
4.0
Chrysene
1.0
4.0
4,4'-DDD
1.5
6.0
4,4'-DDE
1.5
6.0
4,4'-DDT
3.0
12
Dibenzo[a,h]anthracene
1.0
4.0
Di-n-butyl phthalate
5.0
20
1,2-Dichlorobenzene
1.0
4.0
1,3-Dichlorobenzene
1.0
4.0
1,4-Dichlorobenzene
1.0
4.0
3,3'-Dichlorobenzidine
3.0
12
Dieldrin
1.5
6.0
Diethylphthalate
1.0
4.0
Dimethylphthalate
1.0
4.0
2,4-Dinitrotoluene
1.0
4.0
2,6-Dinitrotoluene
1.0
4.0
Di-n-octyl phthalate
1.0
4.0
Endosulfan I
5.0
20
Endosulfan II
5.0
20
Endosulfan sulfate
3.0
12
Endrin
4.0
16
Endrin aldehyde
4.0
16
Fluoranthene
1.0
-------
TABLE 1: MDL/PQL in Water (continued)
Analyte
MDL
PQL
Fluorene
1.0
4.0
Heptachlor
2.0
8.0
Heptachlor epoxide
1.5
6.0
Hexachlorobenzene
1.0
4.0
Hexachlorobutadiene
1.0
4.0
Hexachloroethane
3.0
12
Hexachlorocyclypentadiene
3.0
12
Indeno[ 1,2,3-cd]pyrene
4.0
16
Isophorone
1.0
4.0
Naphthalene
1.0
4.0
Nitrobenzene
1.0
4.0
N-Nitrosodimethylamine
2.0
8.0
N-Nitrosodi-n-propylamine
1.0
4.0
N-Nitrosodiphenylamine
1.0
4.0
PCB-1016
300
1500
PCB-1221
300
1500
PCB-1232
300
1500
PCB-1242
300
1500
PCB-1248
300
1500
PCB-1254
300
1500
PCB-1260
300
1500
Phenanthrene
1.0
4.0
Pyrene
1.0
4.0
Toxaphene
500
2500
1,2,4-Trichlorobenzene
1.0
4.0
4-Chloro-3-methylphenol
1.0
4.0
2-Chlorophenol
1.0
4.0
2,4-Dichlorophenol
1.0
4.0
2,4-Dimethylphenol
3.0
12
2,4-Dinitrophenol
15
60
2-Methyl-4,6-dinitrophenol
3.0
12
2-Nitrophenol
1.0
4.0
4-Nitrophenol
4.0
16
Pentachlorophenol
3.0
12
Phenol
1.0
4.0
2,4,6-Trichlorophenol
1.0
4.0
Carbazole
1.0
4.0
2-Picoline
1.0
4.0
Pyridine
4.0
16
N-N itrosomethylethylamine
2.0
8.0
Methyl methanesulfonate
1.0
4.0
N-Nitrosodiethylamine
1.0
4.0
Ethyl Methanesulfonate
1.0
4.0
Pentachloroethane
100
400
Aniline
1.0
4.0
Benzyl alcohol
1.0
4.0
2-Methyl phenol (O-Cresol)
1.0
-------
TABLE 1: MDL/PQL-Water (continued)
Analyte
MDL
PQL
Acetophenone
1.0
4.0
N-Nitrosopyrrolidine
2.0
8.0
N-Nitrosomorpholine
1.0
4.0
o-Toluidine
1.0
4.0
m,p-Methylphenol (m/p-cresol)
2.0
8.0
N-Nitrosopiperidine
1.0
4.0
2,6-Dichlorophenol
1.0
4.0
4-Chloroaniline
1.0
4.0
Hexachloropropene
4.0
16
N-Nitrosodi-n-butylamine
1.0
4.0
Safrole
1.0
4.0
2-Methylnaphthalene
1.0
4.0
1,2,4,5-Tetrachlorobenzene
1.0
4.0
Isosafrole
4.0
16
2,4,5-Trichlorophenol
1.0
4.0
2-Nitroaniline
1.0
4.0
1,4-Naphthoquinone
100
400
1,3-Dinitrobenzene
2.0
8.0
3-Nitroaniline
1.0
4.0
Pentachlorobenzene
1.0
4.0
Dibenzofuran
1.0
4.0
2-Naphthylamine
40
160
2,3,4,6-tetrachlorophenol
2.0
8.0
1-Naphthylamine
40
160
5-Nitro-o-toluidine
1.0
4.0
4-Nitroaniline
1.0
4.0
Diphenylamine
1.0
4.0
1,3,5-Trinitrobenzene
8.0
32
Phenacetin
1.0
4.0
Pentachloronitrobenzene
3.0
12
4-aminobiphenyl
40
160
Dinoseb
8.0
32
4-Nitroquinoline-l-oxide
8.0
32
Methapyrilene
15
60
p-(dimethylamino)azobenzene
1.0
4.0
3,3'-DimethyIbenzidine
40
160
2-Acetylaminofluorene
2.0
8.0
7,12-dimethyIbenz(a)anthracene
1.0
4.0
3-methylcholanthrene
1.0
-------
Table 2: DFTPP Tuning Criteria
m/z
Ion Abundance Criteria
51
30-60% of mass 198
68
less than 2% of mass 69
69
reference only
70
less than 2% of mass 69
127
40-60% of mass 198
197
less than 1% of mass 198
198
base peak, 100% relative abundance
199
5-9% of mass 198
275
10-30% of mass 198
365
greater than 1% of mass 198
441
0-100% of mass 443
442
greater than 40% of mass 198
443
-------
5/14/98
Revision Date: 04-07-98
Authors: J. Nagle, S.M. Reddy, G. L. Dearman
SV-001-2
jf(\&
Extraction of Base/Neutral and Acid Organic Analytes
from Water
1. SCOPE AND APPLICATION
1.1 This SOP details the extraction of a select group of base-neutral and acid extractable (BNA) analytes from water
matrices for subsequent analysis by GC/MS. These analytes are listed in Table 1.
1.2 BNA extractions are used to isolate up to 150 compounds with a range of boiling points and chemical properties.
Many of these analytes are extremely sensitive to light, heat and active sites on glassware, etc. Analyte recovery may
be significantly reduced if this SOP is not followed closely and carefully.
1.3. This method is based on EPA methods 625 12', 8270B 122 and 3510B 123.
2. SUMMARY OF THE METHOD
2.1 A measured volume of water is serially extracted with methylene chloride at a pH greater than 11 and again at a pH of
less than 2 using separatory funnel technique. The resulting methylene chloride extract is dried and concentrated
using an S-Evap® or Turbo-Vapw' system. The extract is further concentrated to a final volume of 1 mL using an N-
Evap®' system and analyzed by GC/MS. Quantitation by internal standard technique is used.
2.2 If the resulting sample extract contains high levels of high molecular weight compounds, it may be cleaned up using
Gel-Permeation Chromatograpy (GPC).
2.3 Method interferences may be caused by contamination in solvents, glassware, reagents or other sample equipment.
Phthalates are universal contaminants found in lotions, oils, and plastic and can therefore easily be introduced into the
sample extracts. Never touch the interior of any clean glassware. Any aluminum foil used should be used with the
dull side facing the sample extract. NEVER use parafilm. Rinse glassware thoroughly with methylene chloride prior
to use.
3. APPARATUS AND EQUIPMENT
3.1 Glassware
3.1.1 If using the S-Evap® sample concentration system:
3.1.1.1 kuderna-Danish (K&D) concentrator tubes-- 15mL
3.1.1.2. Ground glass stoppers to fit concentrator tubes
3.1.1.3 K&D 500 mL evaporative flasks; attach to concentrator tubes with clips
3.1.1.4 Snyder columns — three ball macro or equivalent
3.1.1 Clips -- used to attach conceniiator tube to K&D flask
3.1.2. If using the Turbo-Vap" sample concentration system: 300 mL concentration vessels with a 0.5 mL or 1.0
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5/14/98
Page 2
3.1.3. Centrifuge tubes, graduated (10-15 mL), with screw caps with Teflon-lined septa
3.1.4 Autosampler vials -- 2 mL, amber, with screw tops with Teflon-lined septa
3.1.5 Erlenmeyer flasks, 500 mL with ground glass mouth and stoppers
3.1.6 Glass powder funnels, approximately 10 cm in diameter, with long stems
3.1.7 1000 mL graduated cylinder
3.1.8 2 liter separatory funnels with Teflon stopcocks and stoppers
3.1.9 Glass Pasteur pipets
3.1.10 Gas-tight micro-syringes or volumetric pipets, 250 uL. 500 llL and 1000 ul.
3.2 Teflon-lined septa for the centrifuge tubes
3.3 Teflon boiling chips
3.4 Large volume (200-500 mL) concentration system
3.4.1 S-Evap -: Consists of heated water bath and water-cooled condensers; capable of concentrating eight sample
extracts simultaneously
OR
3.4.2 Turbo-Vap®': Consists of a warm water bath and chilled water condenser system. Each unit concentrates two
samples simultaneously while unattended.
3.5 N-Hvap®: consists of heated water bath and apparatus to further concentrate the extract using nitrogen gas.
3.6 Top-Loading balance, accurate to 0.1 g.
3.7 Automatic separatory funnel tumbler
3.8 Nitrogen, Zero-Grade, passed through a drying filter at point of use to remove traces of water oi oil
3.9 Shimadm I [PLC AutoPiep s\ stem for GPC cleanup. Phenomenex high performance column (envirosep ABC
350x21.2mm). Mobile phase is methylene chloride.
3.10 Centrifuge to fit 15 mL centrifuge tubes.
4. REAGENTS AND CHEMICALS
4.1. Methylene chloride, Optima or Pesticide grade or equivalent
4.2 Acetone, Optima or Pesticide grade or equivalent
4.3 BNA Surrogate Mix for Water/Sediments (200 ug/mL acids, 100 uu/mL base neutrals). Prepared as in STANDARDS
PREPARATION, SOP # S\ -009.
4.4 BNA Matrix Spike Mix for Water/Sediments (200 ug/mL acids, 100 ug/mL base-neutrals) as prepared in
STANDARDS PREPARATION, SOP ft SV-009. ' "
4..^ Internal standard solution: 400 t^/mL l,4-dichlorobenzene-d4, naphthalene-d8, acenaphthene-dlO, phenanthrene-
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4.6 ION Sodium hydroxide (prepare in hood, using a stirring plate to mix!): Prepare by dissolving 40 g of NaOH in
100 mL reagent water. Transfer to a Teflon storage container.
4.7 Sulfuric acid (1:1) (prepare in hood, using a stirring plate to mix!): Prepare by slowly adding 200 mL concentrated
H2S04 to 200 mL reagent water. Allow to cool, then transfer to glass storage container.
4.8 Granular sodium sulfate: Bake in a muffle furnace at 460° C for at least 8 hours. Allow to cool before using. Store in
a large moulh bottle with cap.
4.9 Glass wool (Silane treated): Bake in a muffle furnace at 460° C for at least 48 hours. Store in an oven at 100° C. Do
not store in plastic.
5. SAMPLE COLLECTION, PRESERVATION, AND HANDLING
5.1 Samples are collected in 1 liter amber glass bottles, transported to the lab on ice and stored at 4° C.
5.2 All water samples must be extracted within seven days after collection.
6. SAMPLE EXTRACTION
NOTE: A SECOND PERSON SHOULD WITNESS THE ADDITION OF SPIKE STANDARD TO THE PROPER
SAMPLES, VERIFY THE CORRECT VOLUME AND CONCENTRATION, AND INITIAL IN THE LOG BOOK.
6.1 Water Extraction for W-BNA/8270
6.1.1 Remove the sample bottles from the receiving room walk-in cooler.
6.1.2 Remove the BNA Spike Mix for Water and Sediments and the BNA Surrogate Mix for Water and
Sediments from refrigerator and let warm to room temperature.
6.1.3 Thoroughly clean all glassware by Musing it with hot tap water, deionized water and acetone, then baking it
in an oven at 450° C lor 6 hours. Alternative!}, glassware may be thoroughl\ washed with Alconox and hot
water, then rinsed with hot tapwatei. dcionized water, and acetone Pre-rinse all glassware with
methylene chloride prior to use!
6.1.4 Assemble one of the following pieces of glassware for each sample:
6.1.4.1 2 L separatory funnel with Teflon stopcock and Teflon stopper
6.1.4.2 500 mL Erlenmeyer flask with ground glass mouth and stopper
6.1.4.3 Two glass powder funnels
6.1.4.4 500 mL Kuderna-Danish flask, column, and concentrator tube or a Turbo-Vap® concentration
vessel.
6.1.4.5 centrifuge tube with Teflon-lined screw cap
6.1.5 Prepare glass powder funnels by placing a small plug of glass wool in the bottom of funnel and topping
with approximately 1-3 cm of muffled granular sodium sulfate. Make sure the sodium sulfate has been
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6.1.6 Rinse the funnel assembly with approximately 10-15 mL of methylene chloride and discard rinsate into
waste beaker.
6.1.7 Label all glassware with the appropriate sample number, using labeling tape or pre-printed sample bar
code labels. (DO NOT USE A PERMANENT MARKER! Methylene chloride will wash off the sample
ID if it contacts the outside of the glassware.) There should be one blank, one laboratory fortified blank
(i.e., reagent water spike — use 11 PLC grade water) and two matrix spikes (duplicates) for each set of
samples extracted, not to exceed 20 samples per set.
6.1.8 Before proceeding, ensure that the samples are at room temperature.
6.1.9 Before proceeding, ensure that the spike and suirogate mixes are at room temperature. Many compounds
easily precipitate out of solution when in the refrigerator or freezer and they need to be re-dissolved into
solution by being wanned to room temperature. Also shake the bottle to ensure complete dissolution.
You may place the capped bottle of solution in a sonic water bath for several minutes to quickly warm up
the solution if you are pressed for time.
6.1.10 Measure the pH of each sample using wide-range pH paper. Be very careful to rinse the glass rod with
acetone between samples to prevent cross contamination, or use a new glass rod or disposable Pasteur pipet
for each sample. Record the value in the extraction notebook.
iN.15.: The extraction notebook is a very valuable reference. Care should be taken that entries for each
sample are complete and accurate. Any unusual observations made during the extraction process,
including sample color or special extraction instructions, should be entered in the notebook.)
6.1.11 Weigh each amber bottle for later determination of volume. Pour the entire sample into the 2 liter
separatory funnel. For the laboratory blank and the duplicate laboratory fortified blanks, use 1000 mL of
HPLC grade water. Choose one sample to spike in duplicate and measure 1000 mL into each of two
separatory funnels. NOTE: If there is insufficient sample to extract two 1000 mL sample matrix
spikes and still have one liter left over for possible re-extractions (i.e., less than 4 liters of sample),
extract one 1000 mL matrix spike and duplicate lab fortified blanks. If only one bottle of sample was
received, extract duplicate lab fortified blanks and save 100 mL of each sample in case of future re-
e\tractions. If less than 2 matrix spikes are extracted, note this in the log book.
6.1.12 Fortify all blanks, samples, and spikes with 500 ill. of the BNA Surrogate Mix for Water/Sediments (200
ug/mL acids, 100 ug/mL base neutrals). Fortify the matrix spikes and laboratory fortified blanks with 250
ul. of the BNA Matrix Spike Mix for Water/Sediments (200 iig/mL acids, 100 iig/mL base neutrals). Note
the amount added and the concentration of analytes in the extraction log book.
N.B.: When adding surrogate and spike mixes, be careful that you do not mix the two up; if you are unsure
whether you have made a mistake in spiking, it is best to simply re-spike a new sample. If there is no more
sample left to re-spike, note the exact amount added so the chemist can make the correct recovery
calculations.
6.1.13 Adjust the pH of each to >11 using 10N NaOH, using narrow-range pH paper to determine pH.
6.1.14 Add 60 mL methylene chloride to each sample. Swirl each separatory funnel gentk to allow NaOH to mix
into sample and allow the vapors to escape before capping. Stopper each funnel and secure the tumbler lid.
6.1.15 Turn on the tumbler slowly for a half turn, stopping with the funnels upside down. Slowly open the
stopcocks to vent the pressure. Close the stopcocks.
6.1.16 Repeat step 6.1.15 at least two more times, turning two full turns then three full turns, before venting.
Continue until the amount of gas escaping is minimal.
6.1.17 Turn on the tumbler again and set the speed to 6 (about 40-50 turns per minute). Tumble for two minutes.
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6.1.19 Remove the stoppers from the separatory funnels and allow the methylene chloride and water layers to
separate for at least 10 minutes.
6.1.20 Drain the bottom layer through the funnel containing glass v\ool and sodium sulfate into a 500 mL
Erlenmeyer flask. Do not allow water to drain through the stopcock. If there is an emulsion, you may add
additional sodium sulfate to the filter funnel and carefully drain it through the funnel. This may introduce
some water into the sample (see 7.1.4 for removing water). If the emulsion is very bad, it may be
necessary to follow one or all of these techniques to break it up:
• Allow separatory funnel to stand for several minutes
• GeiitK agitate emulsion with a long, glass stirring tod
• Remove entire bottom layer of sample and centrifuge to separate water and methylene chloride
• Add more methylene chloride
6.1.21 Rinse the sodium sulfate tunnel liberally with methylene chloride after each layer is drained through.
6.1.22 Extract two more times with 60 mL of methylene chloride following the procedures in steps 6.1.14-6.1.21,
collecting and combining each methylene chloride layer in the Erlenmeyer flask.
6.1.23 After all of the methylene chloride layers have been collected in the flask, rinse the sodium sulfate in the
funnel with 5-10 mL of methylene chloride, draining it into the 500 mL flask. Stopper the flask or cover
with aluminum foil (dull side down facing sample).
6.1.24 Do not use the same sodium sulfate or glass funnel to collect the acid fiaction. Discard the sodium sulfate
(see 6.1.28) and prepare a new funnel with glass w ool and sodium sulfate (see 6 1.5). Otherwise. anaKles
in the acidic fi action may be trapped in the sodium sulfate.
6.1.25 Acidify the samples with 1:1 H2SO4 to below pH 2, using narrow-range pH paper to check pH. THE
ADDITION OF ACID CAUSES A RAPID BUILD-UP OF PRESSURE IN AN ENCLOSED
SEPARATORY FUNNEL. BE SURE TO VENT THOROUGHLY BEFORE BEGINNING THE
TUMBLING PROCEDURE! Extract three times with 60 mL methylene chloride as was done for the
base neutral fraction. If no water was collected in the Erleiimc\er flask, you may collect the acid fraction
in the same Erlenmeyer flask as the base neutral fraction. 11"any water or sodium sulfate is in the flask with
the base ncutial fraction, collect the acid fraction in a separate Crlcnmc>er flask.
6.1.26 After the final extraction, rinse the glass wool/sodium sulfate funnel with 5-10 mL of methylene chloride,
letting it drain into the flask.
6 I 27 Collect the remaining water from all of the separatory funnels into a bucket. The water will be acidic, no
neutralize it with sodium bicarbonate. Dispose of the neutralized water down a sink
6.1.2S Determine the original volume of sample extracted by weighing the amber sample bottles. Assume that the
sample has a density of lg/mL. If in doubt as to the sample density, weigh an exact volume (5-10 mL) to
determine density. Record sample volume to the nearest 10 mL
6.1.2') Discard the contents of the funnels into a pan and allow the methylene chloride to evaporate in a hood
before disposing of the sodium sulfate and glass wool into a trash can. Cap the flasks until ready to
concentrate. Store in the refrigerator if concentration will not be performed within the following two
hours. To concentrate, proceed to section 7.1 for K&D concentration or section 7.2 for Turbo-Vap®
concentration.
6.1.30 Put away all chemicals and wash all glassware so that it is ready for the next set of extractions. Make sure
there is enough sodium sulfate for future extractions; prepare more if there is not. Make sure there are
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6.1.31 Be sure to store spike and surrogate mixes in the refrigerator when not in use. During use, re-cap bottles of
surrogates or spikes as soon as you are done with them in order to minimize evaporation of solvent. Spike
mixes are checked by BNA chemists prior to being allowed into use to ensure that the solution was made
correctly. If you leave solution out overnight, or have any other reason to believe that the solution is no
longer valid, inform the BNA supervisor so that it can be re-checked and/or re-made.
NOTE: If carrying out extraction for the following water analyses, note deviations:
6.2 Extractions for W-BN Analysis
Follow procedure outlined in part 6.1, omitting steps 6.1.24-6.1.25 involving extraction of the acid fraction.
6.3 Extractions for W-AE Analysis
Follow procedure outlined in part 6.1, omitting steps 6.1.13-6.1.24 involving extraction of the base neutral fraction
except as referenced in step 6.1.25.
6.4 Extractions for W-PETHYD Analysis
6.4.1 If the sample looks clear and there is slight or no odor, follow procedure outlined in part 6.1 with the
following exceptions:
6.4.1.1 Do not adjust the pH of the sample. No addition of acid or base is needed. Prepare the blank, lab
fortified blanks and duplicate matrix spikes as in 6.1.12.
6.4.1.2 Extract only three times with methylene chloride as described in the procedure in step 6.1.14-
6.1.23.
6.4.1.3 Glassware used in the extraction of petroleum hydrocarbon samples should be cleaned carefully
with chromic acid before using for any other analyses.
6.4.2. If the sample consists of two phases, such as an oily layer floating on top of an aqueous layer, both layers
must be prepared for analysis separately.
6.4.2.1 Pipet the oily layer into another container. This layer should be extracted using the procedure
outlined for waste samples in SOP # SV-003.
6.4.2.2 Extract the aqueous layer following the procedure in section 6.1.
7. SAMPLE EXTRACT CONCENTRATION
NOTE: Sample extracts may be concentrated using the S-Evaph System (K&D apparatus) or the Turbo-Vap-1 System.
Store all sample extracts in the refrigerator at 43 C until you are actually ready to work with them. If you are not
positive that you can get to the samples within 30 minutes of removal from the refrigerator, then leave them there.
Extracts can go directly from the refrigerator to K&D or to N. blow down without warming to room temperature,
so there is no need to take them out until you are ready to pour them into a K& I) flask or to place them onto the
N: blow-down. Keeping them in the refrigerator until just prior to use will also ensure that the samples are
exposed to as little light as possible. Many BNA compounds are light sensitive and can photo-degrade.
7.1 S-Evap'J System Kuderna-Danish (k<.vl>) Concentration
7.1.1 k&l) water samples between 70° C and 75° C (sediments are concentrated between 75= C and 85= C -- >ee
SV-002). It is best to K&I) samples to a \olume of 3-5 mL instead of to0.5mL-l mL. Concentration can
be completed on the N-Evap - (It is too easy to boil samples dry when you have main' samples on the S-
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7.1.2 An hour or so before concentrating the sample extracts, turn on the S-hvap'®, setting the dial to 5.5 to heat
the water. The water level should be approximately half the depth of the water bath. Cover the holes with
watch glasses to prevent steam from escaping. Be sure the water will not cover the joint between the flask
and the concentrator tube.
7.1.3 Attach the concentrator tube to the Kudema-Danish flask with a plastic clip and add 2-3 Teflon boiling
chips. Label the flask with the sample number.
7.1.4 If water or solid particles are present in the sample extract, remove as follows:
7.1.4.1 If there appears to be water in the sample extract flask, add a small amount of granular sodium
sulfate to the flask and swirl the flask to allow the sodium sulfate to absorb excess water.
7.1.4.1.1 If the water is pH 7 (i.e.. it is from condensation on the glass), no other action needs to
be taken.
7.1.4.1.2 If the water is acidic oi basic (i.e.. it is part of the phi-adjusted sample that has become
mixed with the extract), and both the acid and basic fractions were collected in the
same flask, add sodium sulfate and ddecant the extract into a K&D flask. I hen. use 10
N NaOl I (if the water is acidic), or 1:1112S04 (if the water is basic) to rinse the inside
of the flask. Add a small amount of methylene chloride and swirl the flask. Then,
remove am lemaining water with sodium sulfate and decant the metlu lene chloride
into the K&D flask along with the rest of the extract.
7.1.4.2 If there is a large amount of water in the extract, or both water and solid panicles, place a small
plug of silanized glass wool into the bottom of a clean glass powder funnel and pour 2-3 cm of
granular sodium sulfate on top of it. Carefully pour the sample extract from the Erlenmeyer flask
through the funnel and into the K&D flask If the water in the flask is not neutral, follow step
7.1 4.1.2. Rinse the Erlenmeyer flask three times with 5 mL or so of methylene chloride and
adding that to the funnel. Rinse the funnel with 5-10 mL of methylene chloride.
7.1.4.3 If the extract contains solid particles, but no water, pioceed as in step 7.1.4.2. but omit the sodium
sulfate, hiIter the extract through a glass funnel containing silanized glass wool.
7.1.4.4 Make sure that there is no water or panicles (including sodium sulfate) in the extract before
proceeding.
7.1.5 If the extract w as not transferred into a K&D flask in step 7.1.4. then pour the sample extract from the
hilenmeyer flask into a K&D flask. Rinse the Hilenmeyer flask three times with methylene chloride,
adding the rinsate to the K&D flask.
7.1.6 Pre-wet a three-ball Snyder column by adding about 1 mL methylene chloride to the top. Attach the
column to the K&D apparatus. Place the K&D apparatus on the S-Hvap1^ with the hot water bath between
70° C and 75° C. At the proper rate of distillation the balls of the column will actively chatter, but the
chambers will not flood with condensed solvent. It should take 20-30 minutes to complete the distillation.
It is extremely important that the samples are not concentrated to dryness; if this occurs, a
significant portion of the lighter molecular weight compounds of interest will be lost.
7.1.7 Remove the K&D apparatus from the S-Kvap ^ when there is only 3-5 mL left in the concentrator tube. Do
not let the tube boil dry. Let the vapors in the condensing column cool and drain into the tube, then
remove the Snyder column and rinse the inside of the K&D flask with a few mL of methylene chloride,
allowing this to drain into the concentrator tube. If the sample would not concentrate or is very dark in
color, contact the chemist in charge of the analysis for instructions before proceeding with that sample.
samples, it is vitally important that they not be allowed to go dry. If this occurs, re-e\tract the entire
sample. It is virtually ensured that the QC will be unacceptable if the sample goes dry even for a second.
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7.1.8 Remove the concentrator tube from the K&D flask. There may be water on the outside of the flask -- do
not allow it to drip into the sample (1 he water can be removed with a Kim-Wipe.). Rinse the joint of the
K&D flask with methylene chloride into the concentrator tube.
7 1.9 Proceed to section 7.3 for final extract concentration, or if GPC Cleanup is needed, dilute sample to 10 mL
with methylene chloride and proceed to section 8, GPC CLEANUP PROCEDURE
7.2 Turbo-Vap® Sample Concentration
7.2.1 Before beginning Turbo-Vap® concentration turn on the Turbo-Vap® unit and set the bath temperature to
40° C. Turn on the Isotemp® Refrigerated circulator (the temperature should be preset at about 4° C.).
Check the water level in both units. In the Turbo-Vap®. water should be halfway up the lower set of
perforations in the back of the chamber. In the circulator, the water must at least cover the cooling
elements and may be above them by about two inches. Check the Turbo-Vap® waste bottles to be sure
they will not over fill during concentration. Ensure that the Turbo-Vap® is programmed to stop when a
sensor endpoint is reached.
7.2.2 If there appears to be water or solid particles in the sample extract flask, transfer to the Turbo-Vap® vessel
as in section 7.1.4. Otherwise, transfer the extract to the Tuibo-Vap-' vessel as in section 7.1.5.
7.2.3 Place the vessel in the Turbo-Vap:"' and position condenser/fan assembly over the vessel. Press the start
button for the appropriate vessel (left or right cell). Be sure the solvent waste is draining properly into the
waste bottle. The Turbo-Vap® will signal when the sensor endpoint has been reached and will continue to
signal until the stop button is pushed. Remove the vessel from the 1 urbo-Vap® to prevent further
evaporation. The outside of the condenser may be covered in water droplets. He sure that they do not drip
into the sample extract. If the sample evaporates to dryness, re-c\tract the entire sample.
NOTE: It may be necessary to secure a paper towel around the base of the condenser to prevent condensed
water dripping into the flask.
7.2.4 If the sample would not concentrate to 10 mL or less, is vers viscous, or is very dark in color, contact the
chemist in charge of the analysis for instructions before proceeding with that sample.
7.2.5 Proceed to section 7.3 for final extract concentration or, if GPC cleanup is determined to be necessary,
dilute sample to 10 nil. with meths lene chloride and proceed to section 8, GPC CLEANUP PROCEDURE.
7.3 N-Evap® Concentration
7.3.1 Turn on the N-Evap® water bath and set the dial to around 1.5 so that the water will be warm when
needed; the temperature of the water bath must not exceed 40° C.
7.3.2 Transfer the contents of the concentrator tube or I'urbo-Vap® vessel into a labeled 15 mL screw-top
centrifuge tube using a disposable Pasteur pipet. Rinse the inside of the concentrator tube or Turbo-Vap'®
\ essel thiee times w itli 1 ml. of methylene chloride, and add the rinsate to the centrifuge tube.
7.3.3 Before proceeding with the extraction, contact the chemist who will be analwing the samples. The samples
will need to be transferred to amber 2 ml. autosanipler vials immediate!} upon completion, so the analyst
will need to be reads to do so If the analyst will not be ready to transfer the samples, blow down onls to
approximately 3 ml.. Do not add internal standard C'ap the centrifuge tubes tightly and place them in the
lefngeiaior until the analsst is ready.
7.3.4 Place liie ceiuiituge tubes in the N-hvap'^. I.ossei a needle into each rube, so that the tip of the needle is
appio\iinatels I inch above the surface of the extract. Be sure that the salve-. at the top of the needles that
are in use a;e open 'I uin on the N: stream. Keep the gas flosv at a gentle rate. I he e\tiact should not splash
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7.3.5 Concentrate the samples to a final volume of approximately 0.8 mL using nitrogen/N-Evap® apparatus (it-
possible -- see step 7.3.7); do not let the samples go dry!. If a sample goes dry while on the N-Evap®, re-
extract the entire sample.
7.3.6 If a sample extract is not dark in color or viscous, add 100 uL of the internal standard to the sample and
bring the volume up to 1 mL with methylene chloride. Cap tightly, vortex and centrifuge. After adding
internal standard, give to the analyst immediately. If the sample is dark in color or viscous, but will
concentrate to the correct final \olunie. contact the analyst for specific instructions.
7.3.7 Extracts of water samples should concentrate easily, but if one will not. use the following procedures:
7.3.7.1 If a sample extract will not concentrate to 1 mL, but will concentrate to 5 ml. or below, be sure to
note the final volume on the logsheet. Notify the analyst for special instructions, if any. Take an
aliquot of exactly I ml, of the extract and transfer to a clean, screw-top centrifuge tube. Blow-
down to approximately 0.8 mL. then add internal standard and submit as in step 7.3.6.
7.3.7.2 If a sample extract will not concentrate to 5 ml., bring it to whatever volume is possible. Contact
the anaK st and follow ail} special instructions. Treat the extract as in step 7.3.7.1. However, if
possible, ie-extiact the sample from the start, using an increased volume of spikes and surrogates
proportional to the final volume of the sample (e g.. if a sample will reach a final volume of 10
ml. instead of I mL, re-extract using 5 ml. of surrogate instead of 500 ul..). Submit both extracts.
8. GPC CLEANUP PROCEDURE
8.1 Packing the column: Place approximately 70 g of Bio Beads SX-3 in a 400 mL beaker. Cover the beads with
methylene chloride; allow the beads to swell overnight. Transfer the swelled beads to the column and start pumping
solvent through the column, from bottom to top, at 5.0 mL/min. After 1 hoiu. adjust the pressure on the column to
7-10 psi and pump an additional 4 hours to remove air from the column. Alternatively, use a pre-packed commercial
column with same packing material.
8.2 Calibration of the column: The column is calibrated using an HPLC-UV detector set at 254 nm. Load a 1.5 mL vial of
the GPC Calibration Solution into the autosampler. Attach the outlet flow line from the GPC system to the UV
detector. Inject the calibration solution into the system. Monitor the detector recorder output chromatogram. Note the
retention times for each of the components. The analytes will elute in the following order: Corn oil, bis(2-ethylhexyl
phthalate), methoxychlor, perylene, sulfur.
8.3 The peaks must exhibit the following characteristics:
• Peaks must be observed and should be symmetrical for all compounds in the calibration solution.
• I he corn oil and phthalate peaks must exhibit > 85% resolution.
• The phthalate and methoxychlor peaks must exhibit > 85% resolution.
• The methoxychlor and perylene peaks must exhibit > 85% resolution.
• I he perylene and sulfur peaks must not be saturated and must exhibit >90% baseline resolution.
8.4 Using the information on the elution times, choose a time w indow that will allow collection of effluent just after 85%
of the com oil peak has eluted and just as 15% of the sulfur peak is eluting. Dump time should allow corn oil and
sulfur to be discarded, but not cut into the elution time of the other analytes.
8.5 Filter I nil ol each 10 mL sample extract through 0.45 uni syringe filter into an autosampler vial. After inputting
the correct collect and dump times into the system controller, load the aliquots of each extract onto the autosampler.
I'io;ji am the autosampler to inject I nil of each sample onto the system. If a sample is especially dirt}. you may w ish
to spin the I nil into multiple injections (2 injections of 500 ul.. or 4 of 250 ul.) to prevent bieaktliiough. After
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dump, collect, and wash parameters determined from the calibration, and collect the cleaned extracts in 50 mL culture
tubes that can be sealed with screw-caps. Cap the tubes and stoie them in the refiiterator it'you will not be
concentrating the extract right away. Concentrate the extracts using the N-Kvap^' (see Section 7.3). Transfer each
extract to a centrifuge tube when it has blown down to 1-3 mL. As an alternative for samples that were injected more
than once, you may combine the extracts from the all the vials for one sample, and concentrate by the K&D technique
(section 7.1). or Turbo-Vap® technique (section 7.2). (for Turbo-Vapconcentration).
9. SAMPLE ANALYSIS PROCEDURE
Reference analysis SOP SV-006.
10. QUALITY CONTROL
10.1 For every set of samples (not to exceed twenty samples), a reagent blank, two lab fortified blanks and duplicate matrix
spikes must be prepared. If there is insufficient sample available to prepare duplicate sample matrix spikes, prepare
one reagent blank, two laboratory fortified blanks, and one matrix spike. If theie is insufficient sample available to
piepare a single sample matiix spike, prepaie one reagent blank, two laboratory foitified blanks, and no matrix spike.
10.2 REMEMBER: BNA analytes are very sensitive to many factors. It is easy to become confused during a long BNA
extraction, particularly with a large batch of samples. DO NOT overextend yourself or rush the sample preparation!
Sample holding times are satisfactorily met as long as the extraction into solvent is completed before the sample's
expiration date; you do not have to rush to extract and K&D all in one day, unless you can ensure that the QC is not
being compromised. Minimizing the number of people involved with the extraction and concentration steps can also
keep things from becoming confused.
10.3 Take things slowly and carefully and write down any noted problems or deviations in the extraction notebook. Even
if you believe the deviation will not affect the final result, you may not be aware of how dramatically some of these
changes may affect surrogate and matrix spike recoveries. If you run into technical problems that cannot be answered
by your supervisor, notify the BNA supervisor or the BNA senior chemist immediately for instructions.
10.4 See BNA QA/QC SOP SV-010 for further details.
11. SAFETY/HAZARDOUS WASTE MANAGEMENT
11.1 Wear safety glasses, gloves and a lab coat at all times while performing sample preparation! Methylene chloride will
burn any skin it contacts, so wear nitrile gloves (Latex gloves will not stand up to methylene chloride.).
11.2 Handle all the sample extraction, solvent transfer, concentration, sample preparation, and clean up in a hood at all
times. Avoid breathing metln lene chloride vapors. All extractions MUST be prepared in a fume hood. When not
working directly with samples, pull the hood sash down to the bottom. Do NOT lift the hood sash above the halfway
point (marked with a red line) while tumbling samples.
11.3 All methylene chloride waste should be discarded in the appropriate Chlorinated Waste bottles. Separate chlorinated
and non-chlorinated waste solvents. If mixed, record the volume of each and dispose with chlorinated waste.
11.4 Dispose ot leftover and expired neat standards into a sealed, labeled container.
11.5 Dispose of all the stock standards, working standards and used sample extracts into a Libeled chlorinated waste
container.
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11.7 The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each
chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals
must be reduced to the lowest possible level by whatever means available.
11.8 A reference file of material data handling sheets are kept in a red folder in the GC room. Refer to this folder for any
material you are handling. Update this folder upon receiving new chemicals or reagents.
11.9 Primary standards of these toxic compounds should be prepared in a hood. A NIOSH/MESA approved toxic gas
respirator should be worn when an analyst handles high concentrations of these toxic compounds.
11.10 Dispose of all unwanted, broken glassware into a broken glassware disposal box. Inspect every piece of glassware.
Do not use any that are chipped, cracked, etched, or scratched. Glassware with minor damage should be stored for
repair.
11.11 See Safety-Waste SOP OG-OO1 for further details.
REFERENCES
12.1 Code of Federal Regulations, Title 40, Part 136, Vol. 49, No. 209, Method 625: Base/Neutrals and Acids. 10/26/84.
\2.2Test Methods for Evaluating Solid Wastes, Third Edition, SW-846, Method 8270B. revision 2, 9/94.
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5/14/98
Page 12
Table 1: BNA Analytes
\cenaphthene
Dimethylphthalate
N-Nitrosopiperidine
B^cenaphthylene
1,3-Dinitrobenzene
N-Nitrosopyrrolidine
^cetophenone
2,4-Dinitrotoluene
PCB-1016
2-Acetylaminofluorene
2,6-Dinitrotoluene
PCB-1221
Azobenzene/1,2-Diphenylhydrazine
Di-n-octyl phthalate
PCB-1232
Aldrin
Dinoseb
PCB-1242
4-Aminobiphenyl
Diphenylamine
PCB-1248
Aniline
Endosulfan I
PCB-1254
Anthracene
Endosulfan II
PCB-1260
a-BHC
Endosulfan sulfate
Pentachlorobenzene
b-BHC
Endrin
Pentachloroethane
d-BHC
Endrin aldehyde
Pentachloronitrobenzene
g-BHC
Ethyl methanesulfonate
Phenacetin
p,p'-DDE
Fluoranthene
Phenanthrene
p,p'-DDD
Fluorene
2-Picoline
p.p'-DDT
Heptachlor
Pyrene
Benzo[a]anthracene
Heptachlor epoxide
Pyridine
Benzo[b]fluoranthene
Hexachlorobenzene
Safrole
Benzo[k[fluoranthene
Hexachlorobutadiene
1,2,4,5-Tetrachlorobenzene
Benzo[a]pyrene
Hexachloroethane
o-Toluidine
Benzo[g,h,i]perylene
Hexachlorocyclopentadiene
Toxaphene
Benzyl Alcohol
Hexachloropropene
1,2,4-Trichlorobenzene
Benzyl butyl phthalate
Indeno[l,2,3-c,d]pyrene
1,3,5-Trinitrobenzene
benzidine
Isophorone
4-Chloro-3-methylphenol
Jis(2-chloroethyl) ether
Isosafrole
2-Chlorophenol
fcis(2-chloroethoxy) methane
Methapyrilene
2,4-Dichlorophenol
^is(2-chloroisopropyl)ether
3-Methylcholanthrene
2,6-Dichlorophenol
"Bis(2-ethylhexyl) phthalate
Methyl methanesulfonate
2,4-Dimethylphenol
4-Bromophenylphenyl ether
2-Methylnaphthalene
2,4-Dinitrophenol
Carbazole
Naphthalene
2-Methyl-4,6-dinitrophenol
4-Chloroaniline
1-Naphthylamine
2-Nitrophenol
2-Chloronaphthalene
2-Naphthylamine
4-Nitrophenol
4-Chlorophenylphenyl ether
1,4-Naphthoquinone
Pentachlorophenol
Chrysene
2-Nitroaniline
Phenol
Dibenzo[a,h] anthracene
3-Nitroaniline
2,3,4,6-Tetrachlorophenol
Dibenzofuran
4-Nitroaniline
2,4,5-Trichlorophenol
Di-n-butyl phthalate
Nitrobenzene
2,4,6-Trichlorophenol
1,2-Dichlorobenzene
4-Nitroquinoline-1 -oxide
m.p-cresols
1,3-Dichlorobenzene
5-Nitro-o-toluidine
4-methyl phenol
1,4-Dichlorobenzene
N-Nitrosodi-n-butylamine
2- methyle phenol
3,3'-Dichlorobenzidine
N-Nitrosodiethylamine
o-cresol
Dieldrin
N-Nitrosodimethylamine
Diethylphthalate
N-N itrosodi-n-propylam ine
p-(Dimethylamino)azobenzene
N-Nitrosodiphenylamine
7,12-Dimethylbenz[a]anthracene
N-Nitrosomethylethylamine
3,3'-Dimethylbenzidine
N-Nitrosomorpholine
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5/14/98
Revision Date: 04-07-98
Author: R. Northup, J. Nagle, G. L. Dearman
SV-002-2 . -
Sfl&-
Extraction of Base/Neutral and Acid Organic Analytes
from Sediments
1. SCOPE AND APPLICATION
1.1 This SOP details the extraction of a select group of base-neutral and acid extractable (BNA) analytes
from sediment matrices for subsequent analysis by GC/MS. These analytes are listed in Table 1.
1.2 BNA extractions are used to isolate up to 150 compounds with a range of boiling points and chemical
properties. Many of these analytes are extremely sensitive to light, heat and/or active sites on
glassware, etc. Analyte recovery may be significantly reduced if this SOP is not followed closely and
carefully.
1.3 This method is adapted from EPA method 3550.
2. SUMMARY OF THE METHOD
2.1 A measured weight of sediment is serially extracted with 1:1 methylene chloride:acetone using the
ultrasonic technique. The resulting extract is dried and concentrated using an S-Kvap^ orTurbo-
Vap-1 system. The extract is further concentrated to a final volume of 1 mL using an N-Evap'^
system. Samples aie then ready foi either a Gel Permeation Chromatogy (GPC) clean-up. or for
analysis by GC/MS. Quantitation b> internal standard technique b used.
2.2 Method interferences may be caused by contamination in solvents, glassware, reagents or other sample
equipment. Phthalates are universal contaminants found in lotions, oils, and plastic and can therefore
easily be introduced into the sample extracts. Never touch the interior of any clean glassware. Any
aluminum foil used should be used with the dull side facing the sample extract. NEVER use parafilm.
Rinse glassware thoroughly with methylene chloride prior to use.
3. APPARATUS AND EQUIPMENT
3.1 Glassware
3.1.1 If using the S-Evap® sample concentration system:
3.1.1.1 Kudema-Danish 15 ml. concentrator tube
3.1.1.2 Ground glass stoppers to fit concentrator tubes
3.1.1.3 Kudema-Danish 500 ml. evaporative flask; attaches to concentrator tube with clips
3.1.1.4 Snyder column — three ball macro or equivalent
3.1.1.5 Clips — used to attach concentrator tube to K&l) flask
3.1.2 If using the Turbo-Vap'"- sample concentration system: 300 ml. concentration vessels with a
0.5 ml. or 1.0 ml. sensor endpoint.
3.1.3 Centrifuge tubes, graduated (10-15 mL), with screw caps with Teflon-lined septa
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Page 2
3.1.5 Beakers, 400 mL
3.1.6 Glass powder funnels, approximately 10 cm in diameter, with long steins
3.1.7 Vacuum filtration flasks, 500 mL
3.1.8 Porcelain Buchner funnels, 9 cm
3.1.9 Whatman #4 filter paper, 9 cm
3.1.10 Metal spatulas
3.1.11 Rubber funnel supports
3.1.12 Glass micro-syringes or volumetric pipets, 250 ul., 500 uL and 1000 (.iL,
3.1.13 Glass Pasteur pipets
3.2 Teflon-lined septa for the centrifuge tubes
3.3 Teflon boiling chips
3.4 Large volume (200-500mL) concentration system:
3.4.1 S-Cvap'- : Consists of heated water bath and water-cooled condensers; capable of
concentrating eight sample extracts simultaneously
OR
3.4.2 Turbo-Vap®: Consists of a warm water bath and chilled water condencers; each unit is
capable of concentrating two samples at a time while unattended
3.5 N-Lvap(--': consists of heated water bath and apparatus to further concentrate the extract using nitrogen
gas. The nitrogen should be passed through a drying filter to remove traces of water
3.6 Top-Loading balance, accurate to 0.1 g.
3.7 Nitrogen, Zero-Grade, passed through a drying filter at point of use to remove traces of water/oil
3.8 Sliimad7.ii 11 PLC AutoPrep system fot GPC cleanup. Plienomenex high performance column
(envirosep ABC 350x21.2mm). Mobile phase is methylene chloride.
3.9 Centrifuge to fit 15 ml. tubes
4. REAGENTS AND CHEMICALS
4.1 Methylene chloride, Optima or Pesticide grade or equivalent
4.2 Acetone, Optima or Pesticide grade or equivalent
4.3 BNA Surrogate Mix for Water/Sediments (200 ug/mL acids, 100 ug/mL base neutrals).1 Prepared as in
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5/14/98
Page 3
4.4 BNA Matrix Spike Mix for Water/Sediments (200 lig/mI. acids, 100 ug/ml. base-neutrals) as prepared
in STANDARDS PREPARATION, SOP # SV-009.
4.5 Internal standard solution: 400 ng/mL l,4-dichIorobenzene-d4, naphthalene-d8, acenaphthene-dlO,
phenanthrene-dlO, chrysene-dl2 and perylene d 12- as prepared as in STANDARDS PREPARATION,
SOP# SV-009.
4.6 GPC Calibration Solution.
Prepare a solution in methylene chloride that contains the following analytes in the concentration listed
below:
Analyte mg/mL
corn oil 12.5
bis-2-ethylhexyl phthalate 0.5
methoxychlor 0.1
perylene 0.01
sulfur 0.04
4.7 Sodium sulfate, granular and powder: Bake in a muffle furnace at 460° C for at least S hours. Allow to
cool before using. Store in a large mouth bottle w ith cap.
4 S Glass wool (Silane treated): Bake in a muffle furnace at 460" C for at least 4S hours Store in an oven at
100'C Do not stoie in plastic.
4.9 Ottawa Sand Standard Bake in a muffle furnace at460: C for at least S hours. Allow to cool before
using. Store in a laige mouth bottle w ith cap.
5. SAMPLE COLLECTION, PRESERVATION, AND HANDLING
5.1. Samples are collected in glass jars, transported to the lab on ice and stored at 4 0 C.
5.2 All samples must be extracted within 14 days after collection.
6. SAMPLE EXTRACTION
NOTE : A SECOND PERSON SHOULD WITNESS THE ADDITION OF SPIKE STANDARD TO THE
PROPER SAMPLES. VERIFY THE CORRECT VOLUME AND CONCENTRATION, AND INITIAL
IN THE LOG BOOK.
6.1 Sediment Extraction for S-BNA/8270
This extraction procedure is for samples expected to contain low concentrations of organics (<20
mg/kg). If high concentrations are expected, follow the SOP for waste samples
6.1.1 Cheek out the samples from the reeening loom walk-in cooler.
6 I 2 Remove the BNA Matrix Spike Mis foi Water and Sediments and the UNA Sunogate Mix
tor Water and Sediments tiom refngerator and let them warm to loom temperature.
6.1.3 IhoioughK clean all glassware b\ rinsing it with hoi tap water deioni/'cd water and acetone,
then baking it in an oven at 450c C for 6 hours. Alternatively glasswaie ma> be thoroughly
washed with Alconox and hot water, then rinsed with hot tap water, tieioni^ed water, and
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5/14/98
Page 4
6.1.4 Label all glassware with the appropriate sample number, using labeling tape or pre-printed
sample bar code labels. (DO NOT USE A PERMANENT MARKER! Methylene chloride
will wash off the sample ID if it contacts the outside of the glassware.) There should be one
blank (use Ottawa sand), two laboratory fortified blanks (i.e , Ottawa sand spikes) and two
matrix spikes (duplicates) for each set of samples extracted, not to exceed 20 samples per set.
6.1.5 Note the appearance of the sample in the logbook (e.g., presence of foreign materials,
variable panicle size, etc.).
N.B. The extraction logbook is a very valuable reference. Care should be taken that entries
for each sample are complete and accurate. Any unusual observations made during the
extraction process, including sample color or special extraction instructions, should be
entered in the notebook.
6.1.6 If the samples have not already been homogenized, homogenize each sample by mixing it
thoroughly using a metal spatula. If there is more water present in a sample than you can mix
into the sediment, you ma\ decant it. Do not decant water from the samples at any point
after this step! Remember never to decant water after the dry weight determination has
been made! Kor most samples, you will need to remove the sample from the jar and place it
on a sheet of aluminum foil (dull side up: shiny side down) in order to homogenize it fully.
Remove large rocks or other foreign material (e.g glass, metal, etc.) from the sample at this
time'
6.1.7 Perform a dry weight determination on all samples, unless this has already been done:
6.1.7.1 Weigh 5 g of each sample into a labeled, pre-weighed aluminum weighing dish
Record the weight of the dish and the exact weight of the wet sediment in the dry
weights notebook and dry it overnight at 105° C. The next day. allow it to cool in a
desiccator before weighing it a second time. Record the exact w eight of the dry
sediment in the dry weights notebook
6.1.7.2 To determine a sample's percent solids, divide the dry sediment weight (minus the
dish weight) by the wet sediment weight (minus the dish weight) and multiply by
100%. Enter the wet and dry weights into the computer database.
6.1.8 Using a metal spatula, weigh approximate!) 30 g of each sample into properly labeled 400
ml. beakers. Record the weight in the extraction notebook to the nearest 0.1 g. Weigh out
three 30 g portions of Ottaw a Sand Standard into three 400 mL beakers -- these will serve as
a laboratory blank and two laboratory fortified blanks. Select one sample and weigh out three
30 g portions instead of one - two of these will be used as duplicate matrix spikes. There will
generally be enough sediment in a sample to prepaie duplicate matrix spikes, but if none of
the samples have enough, piepare a single matrix spike or no matrix spike along with
duplicate LFBs and u blank. Re sure to note this in the logbook.
6.1.9 Before proceeding, ensuie that the spike and surrogate mixes are at room temperature. Many
compounds easiK precipitate out of solution u hen in the refi igerator or freezer and they need
to be re-dissolved into solution b> being wanned to room temperature Also shake the bottle
to ensure complete dissolution. You may place the capped bottle of solution in a sonic water
bath foi several minutes to quickly warm up the solution if xon are piessed for time
6.1.10 Add 50(1 u[, of the BNA Surrogate Mix for Water/Sediments (200 ug/ml. acids, 100 ng/ml.
base neutrals) to all samples, blanks, and spikes. Add 250 uL of the BNA Matrix Spike Mix
for Water/Sediments (200 iig/ml acids, 100 ug/ml. base neutrals) to the laboratory fortified
blanks (Ottaw a sand) and to any samples to be used as matrix spikes.). Note the amount
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N.B. When adding surrogate and spike mixes, be careful that you do not mix the two up: if
you are unsure whether you have made a mistake in spiking, it is best to simply re-spike a
new sample. If there is no more sample left to re-spike, note the exact amount added so the
chemist can make the correct recovery calculations.
6.1.11 Add approximately 60 g of sodium sulfate powder to each beaker and mix it into the sediment
with a metal spatula until the sediment appears sandy and free-flowing. If the sample is
already sandy and free-flowing, this step may be omitted.
6.1.12 Add 100 mL of 1:1 methylene chloride:acetone to each beaker.
6.1.13 Cover the beakers loosely with aluminum foil (dull side facing sample) and place them in the
ultrasonic bath. Sonicate for 5 minutes.
6.1.14 Decant and filter the extracts through Whatman No. 42 filter paper in a Buchner funnel into a
clean, labeled 500 mL vacuum filtration flask.
6.1.15 Repeat the extraction (steps 6.1 12-6.1 1-0 two more times with two additional 100 mL
portions of solvent (I. I methylene chloride.acetone). Sonicate for only 3 minutes in each of
these two extractions
6.1.16 After the final sonication, pour the entire sample into the funnel. Rinse the beaker three times
methylene chloride, pouring the rinsate into the funnel Rinse the funnel cake and the sides of
the funnel w ith metln lene chloride
6.1.17. Discaid the contents of the funnels into a pan and allow the solvent to evaporate in a hood
before disposing of the sodium sulfate and sediment into a trash can. Cover the openings of
the flasks w ith aluminum foil until ready to concentrate. Store in the tefrigerator if
concentration will not be performed w ith in the following two hours. I o concentrate, proceed
to section 7.1 for K&l) concentration or section 7.2 for Turbo-Vap^' concentration.
6.1.18 Put away all chemicals and wash all glassware so that it is ready for the next set of
extractions. Make sure there is enough sodium sulfate for future extractions: prepare more if
theie is not. Make sure there are enough methylene chloride-i insed pipets and autosampler
vials, prepare more if there are not.
6.1.1 9 Be sure to store spike and surrogate mixes in the refrigerator when not in use. During use. re-
cap bottles of surrogates or spikes as soon as you are done w ith them in order to minimize
evaporation of solvent. Spike mixes are checked by BN/\ chemists prior to being allowed
into use to ensure that the solution was made correctly If you leave solution out overnight,
or have any other reason to believe that the solution is no longer valid, inform the BNA
supervisor so that it can be re-checked and/or re-made.
6.2 Sediment Extraction for S-PETHYD Analyses
6.2.1 Follow the procedure outlined in 6.1 above for S-BNA/8270.
SAMPLE EXTRACT CONCENTRATION
NOTE: Sample extracts may be concentrated using the S-Evap'- System (k& 1) apparatus) or the Turbo-Vap ®
System. Store all sample extracts in the refrigerator at 4° C' until you are actually ready to work with them. If
you are not positive that you can get to the samples within 30 minutes of removal from the refrigerator, then
leave them there. Extracts can go directly from the refrigerator to k&l) or to N: blow down without warming
to room temperature, so there is no need to take them out until you are ready to pour them into a I) flask or
to place them onto the N2 blow-down. Keeping them in the refrigerator until just prior to use will also ensure
that samples are exposed to as little light as possible. Many BNA compounds are light sensitive and can photo-
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S-Evap® System Kuderna-Danish (K&D) Concentration
7.1.1 K&D soil samples between 75° C and 85° C (water samples aie concentrated between 70°
C and 75c C -- see SV-001). It is best to K&D samples to a volume of 3-5 mL instead of to
0.5 mL-1 mL. Concentration can be completed on the N-Evap®' (It is too easy to boil
samples dry when you have many samples on the S-Evap® at I mL. and are trying to remove
them all before they go dry.). During K&D concentration of samples, it is vitally important
that they not be allowed to go dry. If this occurs, re-extract the entire sample. It is virtually
ensured that the QC will be unacceptable if the sample goes dry even for a second. If the
sample goes dry in the refrigerator, it will also have to be re-extracted.
7.1.2 An hour or so before concentrating the sample extracts, turn on the S-Evap®, setting the dial
to 5.5 to heat the water. The water level should be approximately half the depth of the water
bath. Do not allow water to cover the joint between the K&D flask and the concentrator tube.
Cover the holes with watch glasses to prevent steam from escaping.
7.1.3 Attach the concentrator tube to the Kuderna-Danish flask with a plastic clip and add 2-3
Teflon boiling chips. Label the flask with the sample number.
7.1.4 If water or solid particles are present in the sample extract, remove as. follows:
7 14 1 If there appears to be water in the sample extract flask, add a small amount of
granular sodium sulfate to the flask and swirl the flask to allow the sodium sulfate to
absorb excess water.
7 1.4.2 If there is a large amount of water in the extract, or both water and solid particles,
place a small plug of silanized glass wool into the bottom of a clean glass powder
funnel and pour 2-3 cm of granular sodium sulfate on top of it. Carefully pour the
sample extract from the Erlenmeyer flask through the funnel and into the K&D
flask Rinse the Erlenmeyer flask three times with 5 mL or so of methylene chloride
and adding that to the funnel. Rinse the funnel with 5-10 mL of methylene chloride.
7.1.4.3 I f the extract contains solid particles, but no water, proceed as in step 7.1.4.2. but
omit the sodium sulfate. Kilter the extract through a glass funnel containing silanized
glass wool.
7.1.4.4 Make sure that there is no water or particles (including sodium sulfate) in the extract
before proceeding.
7.1.5 If the extract was not tiansferred into a K&D flask in step 7.1.4. then pour the sample extract
from the Krlenmever flask into a K&D flask. Rinse the Krlenme\er flask three times with
methylene chloride, adding the rinsate to the K&D flask.
7.1.6 Pre-w et a three-ball Snyder column by adding about 1 mL methylene chloride to the top.
Attach the column to the K&D apparatus. Place the K&D apparatus on the S-Evap® with the
hot water bath between 15° C and 85° C. At the proper rate of distillation the balls of the
column will actively chatter, but the chambers will not flood with condensed solvent. It
should take 20-30 minutes to complete the distillation. It is extremely important that the
samples are not concentrated to dryness; if this occurs, a significant portion of the
lighter molecular weight compounds of interest will be lost.
7.1.7 Remove the K&D apparatus from the S-Kvap - when there is only 2-3 mL left in the
concentrator tube. Do not let the tube boil dry. Let the vapors in the condensing column
cool and drain into the tube, then remove the Snyder column and use a Pasteur pipet or rinse
bottle to rinse the sides of the K&D flask with a few mL of methylene chloride, allowing this
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5/14/98
Page 7
color, contact the chemist in charge of the analysis for instructions before proceeding with
that sample.
7.1.8 Remove the concentrator tube from the K.&D flask. There may be water on the outside of the
flask -- do not allow it to drip into the sample ( The water can be removed with a Kiin-Wipe.).
Rinse the joint of the K&D flask with methylene chloride into the concentrator tube.
7.1.9 If the chemist requests cleanup by GPC, dilute sample to 10 mL with methylene chloride and
proceed to section 8 GPC CLEANUP PROCEDURE. If no GPC is required, proceed to
section 7.3 N-EVAP CONCENTRATION.
7.2 Turbo-Vap® Sample Concentration
7.2.1 Before beginning Turbo-Vap ^ concentration turn on the Turbo-Vap® unit and set the bath
temperature to 40° C". Turn on the Isotemp® Refrigerated circulator (the temperature should
be preset at about 4° C.). Check the water level in both units. In the Turbo-Vap®. water
should be halfway up the lower set of perforations in the back of the chamber. In the
circulator, the water must at least cover the cooling elements and may be above them by
about two inches. Check the Turbo-Vap® waste bottles to be sure they will not over fill
during concentration. Ensure that the 'I urbo-Vap® is programmed to stop when a sensor
endpoint is reached.
7.2.2. If there appears to be water or solid particles in the sample extract flask, transfer to the Turbo-
Vap® vessel as in section 7.1.4. Otherwise, tiansfer the extract to the Turbo-Vap® vessel as
in section 7.1.5.
7.2.3. Place the vessel in the I urbo-Vap'''"- and position condenser/fan assembly over the vessel.
Press the start button for the appropriate vessel (left or right cell). Be sure the solvent waste is
draining properly into the waste bottle. The Turbo-Vap® will signal when the sensor
endpoint has been reached and will continue to signal until the stop button is pushed.
Remove the vessel from the Turbo-Vap® to prevent further evaporation. The outside of the
condenser may be covered in water droplets Be sure that they do not drip into the sample
extract. If the sample evaporates to dryness, re-e\tract the entire sample.
NOTE: It may be necessary to secure a paper towel around the base of the condenser to
prevent condensed water dripping into the flask.
7.2.4. If the sample would not concentrate to 10 mL or less, is very viscous, or is very dark in color,
contact the chemist in charge of the analysis for instructions before proceeding with that
sample.
7.2.5. If the chemist requests cleanup by GPC, dilute sample to 10 ml. w ith methylene chloride and
proceed to section 8 GPC CLEANUP PROCEDURE. If no GPC is required, proceed to
section 7.3 N-EVAP CONCENTRATION.
7.3 N-Evap'-1'' Concentration
7.3.1 Turn on the N-Evap'-"' water bath and set the dial to around 1.5 so that the water will be warm
when needed; the temperature of the water bath must not exceed 40° C.
7.3.2 Transfer the contents of the concentrator tube or Turbo-Vap-"'- \essel into a labeled 10-15 mL
sciew -top centrifuge tube using a disposable Pasteur pipet. Rinse the inside of the
concentrator tube or 1 urbo-Vap® sessel three times with I ml. of methylene chloride, and
add the rinsate to the centrifuge tube.
7 3.3 Before proceeding w ith the extraction, contact the chemist w ho w ill be anal> 7ing the samples
I 'tie samples w ill need to be transferred to amber 2 ml. autosanipler \ mis immediately upon
-------
transfer the samples, blow down only to approximately 3 ml.. Do not add internal standard.
Cap the centrifuge tubes tightly and place them in the refrigerator until the analyst is ready.
Place the centrifuge tubes in the N-Hvap1-^. Lower a needle into each tube, so that the tip of
the needle is approximately I inch above the surface of the extract. Be sure that the valves at
the top of the needles that are in use are open. Turn on the N, stream. Keep the gas flow at a
gentle late. '1 he extract should not splash due to the nitrogen flow. Lower the centrifuge tubes
into the water bath.
Concentrate the samples to a final volume of approximately 0.8 mL using nitrogen/N-Evap®
apparatus (if possible -- see step 7.3.7); do not let the samples go dry!. If a sample goes dry
while on the N-Evap®, re-extract the entire sample.
If a sample extract is not dark in color or viscous, add 100 (.iL of the internal standard to the
sample and bring the volume up to 1 mL with methylene chloride. Cap tightly vortex and
centrifuge. After adding internal standard, give to the analyst immediately. If the sample is
dark in color or viscous, but will concentrate to the correct final volume, contact the analyst
for specific instructions.
If an extract will not easily concentrate, use the following procedures:
7 3.7.1 If a sample extract will not concentrate to I ml., but will concentrate to 5 mL or
below, be sure to note the final volume on the logsheet Notify the analyst for special
instructions, if any. lake an aliquot of exactly I ml. of the extract and transfer to a
clean, screw-top centrifuge tube Blow down to approximate!) 0.8 mL. then add
internal standaid and submit as in step 7.3.6.
7.3.7.2 If a sample extract will not concentrate to 5 ml., bring it to w hatever volume is
possible. Contact the analyst and follow any special instructions. Treat the extract as
in step 7.3.7.1. However, if possible, le-extract the sample from the start, using an
increased volume of spikes and suriogates proportional to the final volume of the
sample (e.g.. if a sample will reach a final volume of 10 ml. instead of I mL. re-
extract using 5 ml. of surrogate instead of 500 ul..). Submit both extracts.
GPCCLEANUP PROCEDURE
8.1. Packing the column : Place approximately 70 g of Bio Beads SX-3 in a 400 mL beaker. Cover the
beads with methylene chloride; allow the beads to swell overnight. Transfer the swelled beads to the
column and start pumping solvent through the column, from bottom to top, at 5.0 mL/min. After 1
hour, adjust the pressure on the column to 7-10 psi and pump an additional 4 hours to remove air from
the column. Alternatively, use a pre-packed commercial column with same packing material.
8.2. Calibration of the column: The column is calibrated using an HPLC-UV detector set at 254 nm. Load
a 1.5 mL vial of the GPC Calibration Solution into the autosampler. Attach the outlet flow line from
the GPC system to the UV detector. Inject the calibration solution into the system. Monitor the
detector recorder output chromatogram. Note the retention times for each of the components. The
analytes will elute in the following order: Corn oil, bis(2-ethylhexyl phthalate), methoxychlor,
perylene, sulfur.
8.3 The peaks must exhibit the following characteristics:
• Peaks must be observed and should be symmetrical for all compounds in the calibration
solution.
• I ho vorn oil and phthalate peaks must exhibit > 85% resolution.
• 1 he phthalate and methoxychlor peaks must exhibit > 85% resolution.
7.3.5
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5/14/98
Page 9
• I he methoxychlor and perylene peaks must exhibit > 85% resolution.
• The perylene and sulfur peaks must not be saturated and must exhibit >90% baseline
resolution.
8.4 Using the information on the elution times, chose a time window that will allow collection of effluent
just after 85% of the com oil peak has eluted and just as 15% of the sulfur peak is eluting. Dump time
should allow corn oil and sulfur to be discarded, but not cut into the elution time of the other analytes.
8.5. Kilter 1.5 m L of each 10 mL sample extract through 0.45 um syringe filter into an autosampler vial.
After inputting the correct collect and dump times into the system controler, load the aliquots of each
extract onto the autosampler. Program the autosampler to inject I ml. of each sample onto the system. If
a sample is especially dirty, you may wish to split the I mL into multiple injections (2 injections of 500
j.iL. or 4 of 250 ul.) to prevent breakthrough. After especially dirty samples, run a GPC blank (methylene
chloride) to check for carry-over. Process the extracts using the dump,collect,and wash parameters
determined from the calibration,and collect the cleaned extracts in 50 mL culture tubes that can be sealed
with screw-caps. Cap the tubes and store them in the refrigerator i f yon will not be concentrating the
extract right awa> Concentrate the extracts lining theN-Kvap1'-" (see Section 7.3). Transfer each extract
to a centrifuge tube when it has blown down to 1-3 mL. As an alternative foi samples that were injected
more than once, you may combine the extracts from the all the vials for one sample, and concentrate by
the K&D technique (section 7.1). or Turbo-Vap- technique (section 7.2). (for Turbo-Vap®
concentration).
9. SAMPLE ANALYSIS PROCEDURE
Reference analysis SOP SV-006.
10. QUALITY CONTROL
10.1 For every set of samples (not to exceed twenty samples), a reagent blank, two lab fortified blanks and
duplicate matrix spikes must be prepared. If there is insufficient sample available to prepare prepare one
leagent blank, two laboratory fortified blanks, and one matrix spike. If there is insufficient sample
available to prepare a single sample matrix spike, prepare one leagent blank, two laboratory fortified
blanks, and no matrix spike.
10.2. REMEMBER: BNA analytes are very sensitive to many factors. It is easy to become confused during
a long BNA extraction, particularly with a large batch of samples. DO NOT overextend yourself or
rush the sample preparation! Sample holding times are satisfactorily met as long as the extraction into
solvent is completed before the sample's expiration date; you do not have to rush to extract and K&D
all in one day, unless you can ensure that the QC is not being compromised. Minimizing the number of
people involved with the extraction and concentration steps can also keep things from becoming
confused.
10.3 Take things slowly and carefully and write down any noted problems or deviations in the extraction
notebook. Even if you believe the deviation will not affect the final result, you may not be aware of
how dramatically some of these changes may affect surrogate and matrix spike recoveries. If you run
into technical problems that cannot be answered by your supervisor, notify the BNA supervisor or the
BNA senior chemist immediately for instructions.
10.4. See BNA QA/QC SOP SV-010 for further details.
11.
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Page 10
11.1 Wear safety glasses, gloves and a lab coat at all times while performing sample preparation!
Methylene chloride will bum any skin it contacts, so wear nitrile gloves (Latex gloves will not stand
up to methylene chloride.).
11.2 Handle all the sample extraction, solvent transfer, concentration, sample preparation, and clean up in a
hood at all times. Avoid breathing methylene chloride vapors. All extractions MUST be prepared in a
fume hood. When not working directly with samples, pull the hood sash down to the bottom. Do
NOT lift the hood sash above the halfway point (marked with a red line) while extracting samples.
11.3 All methylene chloride waste should be discarded in the appropriate Chlorinated Waste bottles.
Separate chlorinated and non-chlorinated waste solvents. If mixed, record the volume of each and
dispose with chlorinated waste.
11.4. Dispose of leftover and expired neat standards into a sealed, labeled container.
11.5. Dispose of all the stock standards, working standards and used sample extracts into a labeled
chlorinated waste container.
11.6 Dispose of all used GC-vials conm in iriLi standards or samples into a labeled chlorinated waste
container.
11.7. The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined;
however, each chemical compound should be treated as a potential health hazard. From this
viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever
means available.
11.8 A reference file of material data handling sheets are kept in a red folder in the GC room. Refer to this
folder for any material you are handling. Update this folder upon receiving new chemicals or
reagents.
11.9 Primary standards of these toxic compounds should be prepared in a hood. A NIOSH/MESA
approved toxic gas respirator should be worn when an analyst handles high concentrations of these
toxic compounds.
11.10 Dispose of all the unwanted, broken glassware into a broken glassware disposal box. Inspect every
piece of glassware. Do not use any that are chipped, cracked, etched, or scratched. Glassware with
minor damage should be stored for repair.
11.11. See Safety-Waste SOP OG-OOl for further details.
12. REFERENCES
12.1. EPA SW846 Methods 3550 (rev. 9/94), 3580 (rev. 7/92) and 8270B (9/94).
-------
Revision Date: 10/97
Author: S. Madhava Reddy, Margaret. Clague, Mohammad GhafTari
GC-002-1
EXTRACTION OF ORGANOPHOSPHORUS, ORGANONITROGEN AND ORGANOHALIDE
PESTICIDES AND PCBS FROM WATER, WASTES, SEDIMENT/SOILS AND FILTERS FOR
SUBSEQUENT ANALYSIS BY GC-ECD/NPD/FPD/FID/MS
1. SCOPE AND APPLICATION
1.1 This method describes the extraction from waters, sediment/soils, filters and wastes of
select organophosphorous, organonitrogen, organohalide pesticides and PCB's. It is based
on EPA Methods 608,614, 617, 619, 3500, 3510, 3540, 3550, 3580, 3620, 3640, 3660,
and 3665.
1.2. The sample extraction and concentration steps in this method are essentially the same for
both halogenated and nitrogen phosphorus containing pesticides. Thus in many
instances, a single sample extraction may recover nitrogen, phosphorus, and halogen-
containing pesticides.
2. SUMMARY OF THE METHOD
2.1. For water samples, a whole one liter bottle of sample is serially extracted with methylene
chloride. The resulting extract is concentrated and solvent exchanged into the
appropriate solvent The sample extract is then ready for analysis by capillary gas
chromatography with electron capture, nitrogen-phosphorus, flame photometric or mass
spectrometric detection.
2.2. For sediment samples, thirty grams of sample is extracted with a 1:1 solution of
methylene chloride:acetone. The resulting extract is exchanged to the proper solvent and
concentrated. The sample extract is then ready for analysis by capillary gas
chromatography with electron capture, nitrogen-phosphorus, flame photometric or mass
spectrometric detection. Samples are further cleaned up by GPC and 1 g Florisil
cartridge for halogenated pesticides.
2.3. For waste samples, one gram of sample is weighed into a calibrated tube and diluted to
10 mL with iso-octane. The resulting extract is then subjected to the appropriate clean up
procedures. The sample extract is then ready for analysis by capillary gas
chromatography with electron capture, nitrogen-phosphorus or flame photometric
detection.
2.4. Filter samples are extracted by Soxhlet extraction using methylene chloride and made up
to 0.5 mL in toluene and analyzed by capillary gas chromatography with nitrogen-
phosphorus detection.
2.5. Any sample extract may undergo a GPC, sulfur, Florisil or sulfuric acid clean up if
necessary.
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3.1. Separatory funnels - 2 L and 1 L with Teflon stopcocks and caps.
3.2. 125 mL & 250 mL Erlenmeyer flasks with B24/40 Std. joint with stopper.
3.3. Graduated cylinders 100 mL and 2 L.
3.4. Concentrator tube, Kuderna-Danish 10 ml-15 mL, graduated with ground glass stopper.
3.5. Evaporative flask, K&D-500 mL, attached to concentrator tube with clips.
3.6. Snyder column, K&D - three ball macro.
3.7. Centrifuge tubes - 10 to 15 mL with standard joint B, or screw cap.
3.8. Boiling chips - approximately 10/40 mesh.
3.9. S-Evap Sample Concentration system (or water bath - with temperature control +/- 2 °C,
capable of holding 500 mL K&D apparatus).
3.10. Separatory funnel tumblers with speed control.
3.11. Balances
3.11.1. Analytical, accurate to 0.000lg.
3.11.2. Top-loading, accurate to 0.1 g.
3.12. Glass stirring rods (long enough to fit down into a 2 liter separatory funnel).
3.13. Ultrasonic water bath.
3.14. Centrifuge (for centrifuging 500 mL bottles and 15 mL tubes).
3.15. Metal spatulas.
3.16. Beakers, 400 ml.
3.17. Volumetric pipets, 0.5,1,2,5,10 ml.
3.18. Volumetric flasks, 10, 25, 50, 100, 200, 250, 500, 1000 ml.
3.19. Disposable Pasteur pipets.
3.20. N-EVAP, nitrogen-sample concentrator.
3.21. GPC:
3.21.1 ' Autosampler: Shimadzu SIL-10A with SCL-10A System controller.
3.21.2 Fraction Collector: Shimadzu FRC-10A. ORFoxy200.\ I":
3.21.3 GPC column: Waters Envirogel GPC clean up column (19X300mm) with
(19X150mm) precolumn. OR Phenomenex Envirosep ABC (350X21.2mm)
with (60X21.2mm) precolumn.
GC-002-l.DOC
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3.22. Glass wool
3.23. Buchner funnels, 9cm.
3.24. Filtration flasks, 500 mL with rubber adapter.
3.25. Whatman 42 filtration circles 9 cm.
3.26. Aluminum weighing pans, for dry weight determination
3.27. Brinkman Dispensette 20-100 mL or a Tippet dispenser with a 60 mL bulb.
3.28. Long stem powder funnel.
3.29. G lass extraction columns.
3.30. Aluminum foil
3.31. Culture tubes 16X150mm and 25X150 mm(50 ml)
3.32. 254-nm fixed wavelength ultraviolet detector.
3.33. Round bottom flask with B24/40 Std. joint - 500 ml
3.34. Soxhlet extractor- ROT-X-TRACT, Organomation.
3.35. Soxhlet extractor body with 55/50 top joint and 24/40 bottom joint
3.36. Drying column - Chromatographic column, approximately 400 mm long x 19 mm ID
with coarse frit filter disc.
3.37. Chromatographic column - 400 mm long x 22 mm ID, with Teflon stopcock and coarse
frit filter disc.
4. REAGENTS AND CHEMICALS
4.1. Reagent water - Deionized water.
4.2. Well water - Free of interferences, used for laboratory blanks and laboratory fortified
blanks
4.3. Solvents
4.3.1. Methylene chloride - Fisher Scientific Pesticide grade
4.3.2. Hexane - Fisher HPLC Grade or Baxter UV or GC/MS Grade.
4.3.3. Toluene, Fisher HPLC Grade or Baxter UV or GC/MS Grade
4.3.4. Acetone - Fisher Pesticide Grade.
4.3.5. Benzene, Fisher Optima or Pesticide/GC-MS grade
GC-002-I.DOC
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4.3.6. Iso-Octane Fisher Scientific, Pesticide Grade
4.4. Sodium Sulfate - (ALS) granular and powder, anhydrous. Purify by heating at 460 °C
for 8 hours or overnight, and store in a largemouth bottle with cap.
4.5. Sodium Thiosulfate - (ACS) Granular
4.6. Florisil cartridge 1 g (6 ml) - Sep-Pak Vac Florisil Cartridge, J&W brand or equivalent
4.7. Tetrabutylammonium hydrogen sulfate, AR.
4.8. Sodium sulfite, AR.
4.9. Mercury - Triple distilled
4.10. Copper powder - activated
4.11. GPC calibration solution: Prepare a solution in methylene chloride that contains the
following analytes in the concentration listed below :
Analvte mg/ml
corn oil 12.5
bis-2-ethylhexyl phthalate 0.5
methoxychlor 0.1
perylene 0.01
sulfur 0.04
4.12. Sodium chloride - AR.
4.13. Sulfuric acid, concentrated.
4.14. Diethyl ether - Fisher AR.
4.15. Sodium hydroxide (NaOH ) solution (10N)- Dissolve 40 g of NaOH(ACS) in DI water
and dilute to 100 ml.
4.16. Florisil, pesticide grade : PR grade (60/100 mesh ). Purchase activated at 1250 °F and
store in the dark in glass containers with ground glass stoppers or foil lined screw caps.
Before use, activate each batch at least 16 h at 130 °C in a foil covered glass container
and allow to cool.
4.16.1. Dry Florisil over night in a oven at 130 °C and cool it to room temperature.
4.16.2. Deactivated Florisil - Weigh 97.5 grams of Florisil and add 2.5 mL or grams
of DI water and mix well.
4.16.3. Store in a tightly sealed container at room temperature.
4.17. Neutral Alumina : Woelm, neutral: deactivated by pipeting 1 mL of distilled water into
125 mL ground glass stoppered Erlenmeyer flask. Rotate flask to distribute water over
surface of glass. Immediately add 19 g fresh Alumina through small powder funnel.
Shake flask containing mixture for 2 h on a mechanical shaker.
GC-002-l.DOC
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4.18. Silica gel: Activated approximately 100 g of silica gel at 200 °C for 16 h in a tarred 500
mL Erlenmeyer flask with ground glass stopper. Allow to cool to room temperature, and
determine the weight of the silica gel. Deactivated by adding 3% by weight of distilled
water. Re-stopper the flask, and shake on a wrist action shaker for at least 1 h. Allow to
equilibrate for 3 or more hours at room temperature.
4.19. Spiking solutions (see standards preparation procedure for more details) (Unless
otherwise noted, volumes listed are to be used if the final volumes of the sample extracts
is to be 10 nil. If the final volume of the sample extract will not be 10 mL. adjust the
volume of the spike accordingly.). Also refer to spike rotation table once a month.
4.19.1. NPD/ECD surrogate spiking solution: 2.5- 4.75 ng /ul TMX/DCB and 50 ng/ul
NPD — use 100 ul
4.19.2. NPD/ECI) surrogate spiking solution 10 times diluted. 0.25-0.475 ng-'ul
TMX/DCB and 5.0 ng/ul NPD -- use 200 ul for Group AA water samples if the
final volume of the sample extract is to be 2 ml.
4.19.3. NPD matrix spike solutions;
4.19.3.1. NPD-A
4.19.3.2. NPD-B
4.19.3.3. NPD-C
4.19.3.4. NPD-D
0.5-2.0 ng /ul use 1 ml
1.0-8.0 ng /ul use 1 ml
1.0-10 ng /ul use 1 ml
for waters: 2.0-12.0 ng /ul use 1 ml
0.8-1.6 ng /ul use 0.5 ml
4.19.3.5. NPD-E
4.19.4. ECD matrix spike solutions;
4.19.4.1. ECD-A + C: 0.5-2.0 ng/ul use 0.5 ml
4.19.4.2. ECD-B: 1.0-4.0 ng/ul use 0.5 ml
4.19.4.3. PCB1016& 1260: 5.0 ng/ul use 1.0 ml
4.19.4.4. Chlordane Tech. & Toxaphene: 5.0 ng/ul use 1.0 ml
4.19.5. Fluoridone spike solution: 2.0 ng /ul use 2.0 ml
4.19.6. Prodiamine spike solution: 10 0 ng /ul use 0.10 ml
4.19.7. femephos spike solution. 0.5 ng /ul use 0.50 nil
4.19.8. Fenamiphos Mix spike solution. 0.5-2.0 ng/ul add 1 mL for 1 mL final volume.
4.19.9. Flusilazole mix spike: 0.5-2.0 ug/ml use 0.5 mL for water and 2.5 mL for soil
5. SAMPLE COLLECTION, PRESERVATION, AND HANDLING
5.1. Water samples are collected in one liter, glass amber bottles with Teflon-lined screw
caps. They are stored at 4° C. All water samples must be extracted within 7 days of
collection.
5.6. Sediment sample-, are collected in 250-500-1000 mL glass jars with Teflon-lined screw
caps. Samples are stored at 4° C. All sediment samples must be prepared within 14 days
of collection.
GC-002-l.DOC
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5.7. Waste samples may be collected in a variety of containers, depending on the nature of the
waste. All samples are stored at 4° C. and must be extracted within 14 days of collection.
5 8. Kilter samples are collected in 250-500 mL glass jais with Teflon-lined screw caps.
Samples are stored at 4° C and must be extracted within 14 da\s of collection.
6. WATER SAMPLE PREPARATION PROCEDURE
NOTE : A SECOND PERSON SHOULD WITNESS THE ADDITION OF SPIKE
STANDARD TO THE PROPER SAMPLES AND VERIFY THE CORRECT VOLUME
AND CONCENTRATION, AND INITIAL IN THE LOG BOOK.
6.1. ROUTINE CHLORINATED/NITROGEN PHOSPHORUS PESTICIDES and PCB's
6.1.1. Weigh the sample bottle before and after taking your sample aliquot or mark the
water meniscus on the side of the sample bottle for later determination of
sample volume. Pour the entire sample into a 2-liter separatory funnel. Use 1L
of well water for blanks and laboratory fortified blanks. (When weighing,
assume sample has a density of 1.0 g/ml. If in doubt, i.e., if sample contains a
significant amount of oils or solvent, weigh an exact volume, 5-10 mL to
determine density.).
6.1.2. Using a clean glass rod or pasteur pipet. transfer a few diops of the sample to a
piece of wide range pH paper. Record pi I in the log book.
6.1.3. Add ECD/NPD surrogate spike mix to all samples (100 ul). Add required
matrix spikes (check work order for specifics) to the laboratory fortified blanks
and matrix spikes.
6.1.4. Add 60 mL of methylene chloride to the sample bottle, and swirl for 30 seconds
to rinse the inner surface. Transfer this rinsate to the separatory funnel.
6.1.5. Stopper each funnel and secure the tumbler lid.
6.1.6. Turn on the tumbler slowly for a half tum, stopping with the funnels upside
down. Slowly open the stopcocks to vent the pressure. Close the stopcocks.
6.1.7. Repeat step 6.1.6 at least Uvo more times, turning one full turn then two full
turns then three full turns, respectively, before venting. Continue until the
amount of gas escaping is minimal.
6.1.8. Turn on the tumbler again and set the speed to 6 (about 30-40 turns per
minute). Tumble for three minutes.
6.1.9. Stop the tumbler with the funnels upright (stopcocks down) and lock it in place.
6.1.10. Remove the stoppers from the separatory funnels and allow the methylene
chloride and water layers to separate for at least 10 min. If an emulsion forms,
follow one or all of these techniques to break up:
GC-002-t.DOC
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• Allow separatory funnel to stand several additional minutes;
Gently agitate emulsion with a long glass stirring rod;
• Sonicate the emulsion;
• Centrifuge the emulsion;
Add solid NaCl and shake;
Add more methylene chloride;
Filter emulsion through glass wool.
6.1.11. Filter the methylene chloride layer through an extraction column fitted with a
glass wool plug into a 250 mL Erlenmeyer flask. Rinse the funnel with 4-6 mL
methylene chloride and collect through the same column.
6.1.12. Repeat steps 6.1.6.- 6.1.11. for a total of three extractions
6.1.13. Rinse the extraction column into the flask with 10-20 mL of methylene chloride.
6.1.14 lfan\ water is collected, tiy to remove it in one of the following ways:
• Pour the extract back into the same separatoiy funnel, and collect the
bottom (organic) layer. Rinse the top (aqueous) layer w ith a few
milliliters of methylene chloride, and collect the bottom layer again.
• Use a pasteur pipet to remove the top (aqueous) layer.
• Sprinkle granular Na:SO, into the extract to nap the water droplets.
Carefully decant methylene chloride layer into K&D set up with out
NiuSO,. Rinse flask three times w ith 5 ml. of methylene chloi ide and
add it to the K&l) set up.
6.1.15. Assemble a Kuderna-Danish (K-D) concentrator by attaching a 15 mL
concentrator tube to a 500 mL evaporative flask, using clips to attach. Rinse the
assembly with methylene chloride and discard the rinsate.
6.1.16. Prewet a Snyder column by adding about 1 mL of methylene chloride to the top.
6.1.17. Transfer extract into K-D, using methylene chloride to rinse the flask three
times. Add one or two clean boiling chips to the evaporative flask and attach a
three-ball Snyder column.
6.1.18. Place the K-D apparatus on a hot water bath (70° C ) so that the concentrator
tube is partially immersed in the hot water.
6.1.19. Concentrate to 3-4 mL then remove K-D apparatus from water bath and allow it
to cool.
6.1.20. Carefully disconnect Snyder column, then rinse flask with 1 or 2 mL of
methylene chloride into tube. Carefully disconnect K&D flask from tube.
MAKE SURE CONCENTRATOR TUBE IS LABELED WITH ITS CORRECT
SAMPLE NUMBER!!
6.1.21. Setup N-EVAP by turning on nitrogen-gas, heater (40 deg C bath temperature
set to about 1.5), and attaching clean needles.
GC-002-l.DOC
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6.1.22. Open valves for each needle and check for required flow of Nitrogen with
blank solvent in a centrifuge tube.
6.1 23. To concentrate in a centrifuge tube, transfer the extract to the centrifuge tube
with a pasteur pipet. Rinse the concentrator tube twice with I mL. of methylene
chloride and once with I ml. of iso-octane or the final volume solvent, each
time transferring the rinse to the centrifuge tube.
6.1.24. Place concentrator or centrifuge tubes into N-Evap tray, then carefully pull
needles down to approximately 2 inches from solvent level. Make sure N2 flow
is adequate, but be careful NOT to blow N2 to vigorously into sample, causing
splashing.
6.1.25. Concentrate to 0.5 mL (it takes about 20 to 30 min.).
6.1 26. Add I mL of iso-octane and N-blow down to 0.5 ml., and repeat with I mL
moie iso-octane and make up to 10 ml. in iso-octane.
6.2. FENAM1PHOS, FENAMIPHOS SULFOXIDE & SULFONE AND FLUORIDONE
Extract as in section 6.1 ROUTINE CHLORINATED/NITROGEN PHOSPHORUS
PESTICIDES and PCB's with the following changes:
6.2.1. Add 100 ul of ten times diluted ECD/NPD surrogate spike to all samples in the
set.
6.2.2. After K&D concentration, transfer the sample extract directly 10 a centrifuge
tube, rinse the concentrator tube two times with 1 mL, of meth\lene chloride and
once u ith I ml. of toluene, transferring the rinse to the centrifuge tube each
time Ik careful not 10 add moie than I ml. of toluene, as toluene has a high
boiling point, and w ill take a long time to concentrate
6.2.3. Blow' down with N-K\ ap to 0.5 ml.
6.2.4. Make up to 1 mL using toluene. There is 110 need (o add more toluene and
blow down more than once, as you would with iso-octane.
6.2.5. Alternatively, same extract prepared for Pesticides analysis in 6.1 may be shared
for W-FEN and W-Fluoridone.
6.3. EXTRACTION OF WATER SOLUBLE PESTICIDES : METHAMIDOPHOS,
ACEPHATE, MONOCROTOPHOS AND DIMETHOATE.
Extract as in section 6.1 ROUTINE CHLORINATED/NITROGEN PHOSPHORUS
PESTICIDES and PCB's with the following exceptions:
6.3.1. \\ eigh 35 g of NaCI and ti ansfer into all. separatory funnel. Measure 100 mL
of well mixed water sample with a graduated cylinder, and add to the separator)-
funnel containing the \;aCI. Tumble for 5-30 mimiies to dissolve all the NaCI
GC-002-l.DOC
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6.3.2. Spike at this stage with 0.5 ml. of NPD MIX-E-SPK (0.8-1.6 ppm) into
laboratory fortified blanks and matrix spikes. Add to all samples in the set 200
ul of ten times diluted ECD/NPD surrogate mix.
6.3.3. When adding the 60 mL of methylene chloride to the sample, add it w ith the
graduated cylinder originally used to measure the sample.
6.3.4. After K&D concentration, transfer extract directly into a centrifuge tube and
rinse the concentrator tube with two times 1 mL of acetone.
6.3.5. Blow down on N-F.vap to 0.5 mL and make up to 2 mL final volume with
acetone.
6.4 EXTRACTION OF CHLORINATED/NITROGEN PHOSPHORUS PESTICIDES and
PCB's WITH LOWER DETECTION LIMITS (GROUP AA)
Extract as in section 6.1 ROUTINE CHLORINATED/NITROGEN PHOSPHORUS
PESTICIDES and PCB's with the following exceptions:
6.4.1 When spiking, use spike mixtures which have been diluted by a factor of ten
(see section 4.19.2 for NPD BCD surrogate).
6.4.2 Before transferring the sample extiact (after K&D concentiationj to a centrifuge
tube, calibrate the tube to 2 ml. and to I ml. Add exactly I ml. of liquid to an
empty, dry. graduated centi ifuge tube Note where the meniscus is (For
example, if 1.0 ml. of liquid tills the tube to the 1.1 ml. graduation mark, you
might write this on the side of the tube as I.I'1.0.). Add exactly I ml. of liquid
again, and note the meniscus a second time. When making to a volume of I or
2 ml. in this tube, use the memscuses that \ou have marked rather than the
original graduations on the tube
6.4.3 Concentrate to 2 nil. in meth\ lene chloride. For FCD. all samples in the set
filter I ml., out of 2 ml. extract through 0.45 um fiIrer into a 1.1 ml.
Autosamplei vial and inject 0 SO ml. on GPC column for cleanup (see sec. 10.3)
followed by I gram Florisil cleanup (see sec 10.4) and make up to 0.S0 nil, in
calibiated centrifuge tube with iso-octane. For NPD. the remaining I mL
extract in the oiiginal centi ifuge tube, add 1 ml. iso-octane and N-blow down to
0.5 ml. and make up to I ml. in iso-octane.
6.5 METHOPRENE
Extract as in section 6.1 ROUTINE CHLORINATED/NITROGEN PHOSPHORUS
PESTICIDES and PCB's with the following exceptions:
6.5.1. Rinse the concentrator tube with methy 1-tert-buty 1 ether (MTBE) when
transferring to the centrifuge tube after K&D concentration.
6.5.2. Final volume after nitrogen blow-down is 1 mL MTBE.
6.6. WATER SAMPLES EXTRACTION FOR FLUSILAZOLE AND ITS METABOLITES,
AND DIBUTYL UREA
GC-002-l.DOC
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Extract as in section 6.1 ROUTINE CHLORINATED/NITROGEN PHOSPHORUS
PESTICIDES and PCB's with the following changes:
6.6.1. After K&D concentration, transfer the sample extract directly to a centrifuge
tube, rinse the concentrator tube two times with 1 mL of methylene chloride and
transferring the rinse to the centrifuge tube each time.
6.6.2. Nitrogen blow down with N-Evap to 0.9 mL and add 25 ul of 10 ug/ml TPP
internal standard and make up to 1 mL with methylene chloride.
6.6.3. If necessary do GPC cleanup on the 1 mL extract before adding TPP internal
standard. For most of the water extracts no cleanup is required.
6.6.4. Alternatively, same extract prepared for Pesticides analysis in 6.1 may be shared
for W-Fluz analysis.
6.6.5. Submit for GC/MS analysis.
7. SEDIMENT SAMPLES
NOTE : A SECOND PERSON SHOULD WITNESS THE ADDITION OF SPIKE
STANDARD TO THE PROPER SAMPLES AND VERIFY THE CORRECT VOLUME
AND CONCENTRATION, AND INITIAL IN THE LOG BOOK.
7.1. ROUTINE CHLORINATED/NITROGEN PHOSPHORUS PESTICIDES and PCB's
7.1.1. Decant and discard any standing aqueous phase. Transfer whole jar of sediment
sample onto a clean aluminum foil. Mix sample thoroughly, especially
composite samples. Discard any foreign objects such as sticks, leaves and
rocks. Transfer the sample back to original bottle with no more than 3/4 full.
IF SAMPLE IS RE-EXTRACTED SECOND TIME, MIX WELL WITHIN
THE BOTTLE AND WEIGH OUT SAMPLE FOR EXTRACTION. DO
NOT DISCARD ANY STANDING WATER, ROCKS, STICKS OR
ANYTHING.
7.1.2. Weigh 5 g of sediment into a pre-weighed aluminum weighing pan (labeled
with sample number) and record weight of boat and sample+boat. Dry
overnight at 105 C to determine the dry sediment weight on the following day
and record weight of dry sample+boat. Prepare excel sheet to report % solids.
7.1.3. Weigh approximately 30 g ± 0.3 g of sediment sample into a 400 mL beaker.
Record weight as 30 g.
7.1.4. Add NPD/ECD surrogate spike mix to all samples (100 ul). Add required
matrix spikes (check work order for specifics) to the Laboratory Fortified
Blanks and Matrix Spikes
7.1.5. Add 60 g anhydrous powdered sodium sulfate and mix well. Wet samples
should be mixed more frequently than dry samples, until they are sandy and free
flowing. DO NOT ADD MORE Na,SO,.
7.1.6. Immediately add 100 mL of 1:1 methylene chloride:acetone to the sample and
cover with aluminum foil. Sonicate for three minutes.
GC-002-l.DOC
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7.1.7. Set up for vacuum filtration using a 500 mL filtration flask, 9 cm Buchner
funnel and Whatman number 42 9-cm filter paper. Rinse the filtration setup
with methylene chloride and discard the solvent to waste.
7.1.8. Decant the sample extract through the Whatman # 42 filter paper.
7.1.9. Repeat steps 7.1.6.-7.1.8. two more times, filtering extracts through the Buchner
funnel and collecting in flask. After the third time transfer the sediment from
the beaker to the Buchner funnel.
7.1.10. Rinse the beaker, funnel and soil cake with methylene chloride, adding rinses to
flask.
7.1.11. Assemble a Kuderna-Danish (K-D) concentrator by attaching a ! 5 mL
concentrator tube to a 500 mL evaporative flask, using clips to attach. Rinse the
assembly with methylene chloride and discard the rinsate.
7.1.12. Prewet a Snyder column by adding about 1 mL of methylene chloride to the top.
7.1.13. Transfer extract into K-D, using methylene chloride to rinse the flask three
times 5 ml. each. Add one or two clean boiling chips to the evaporative flask
and attach a three-ball Snyder column.
7.1.14. If any solid particles are present in the extract, then filter thiough Na,SO|
funnel. If any water droplets are separated, then sprinkle granular Na-,SO, into
the extract to trap the water droplets. Carefully decant into K&D set up with out
collecting Na:SO|. Rinse flask three times with 5 ml. of methylene chloride and
add it to the K&D set up.
7.1.15. Place the K-D apparatus on a hot water bath (80 to 85° C ) so that the
concentrator tube is partially immersed in the hot water.
7.1.16. Concentrate to 3-4 mL then remove K-D apparatus from water bath and allow it
to cool.
7.1.17. Carefully disconnect Snyder column, then rinse flask with 1 or 2 mL of
methylene chloride into tube. Carefully disconnect K&D flask from tube.
MAKE SURE CONCENTRATOR TUBE IS LABELED WITH ITS CORRECT
SAMPLE NUMBER!!
7.1.18. Setup N-EVAP by turning on nitrogen-gas, heater (40 deg C bath temperature
set to about 1.5), and attaching clean needles.
7.1.19. Open valves for each needle and check for required flow of Nitrogen with blank
solvent in a centrifuge tube.
7.1.20. Place concentrator oi centrifuge tubes intoN-Evap tray, then carefully pull
needles down to approximately 2 inches from solvent level. Make sure N2 flow
is adequate, but be careful NOT to blow N2 to vigorously into sample, causing
splashing.
GC-002-l.DOC
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7.1.21. Transfer the extract to the centrifuge tube with a Pasteur pipet. Rinse the
concentrator tube twice with I ml, of methylene chloride and N-blow down to 2
ml. and make up to 10 ml. in methylene chloride.
7.1.22. For GPC cleanup (mandatory for ECD analysis), filter 2 mL of above extract
through 0.45 um filter into a 2 mL Autosampler vial and inject 1 mL (see sec.
10.3) (for bad samples make 1 to 4 injections out of 1 ml). Concentrate and
solvent exchange into iso-octane and do lg Florisil cleanup and make up to 1
mL in iso-octane for ECD (see sec. 10.4).
7.1.23. For NPD analysis take 2 mL of extract out of 10 mL and add 1 mL of iso-octane
and N-blow down to 0.5 mL and make up to 2 mL in iso-octane.
7.1.24. If the sample is being extracted for NPD analysis only, then add 1 mL of iso-
octane in step 7.1.21 and N- blow down to 0.5 mL and make up to 10 mL in iso-
octane.
7.1.25. If the sample is for PCB and Toxaphene only then take 2 mL of sample extract
in iso-octane for sulfuric acid cleanup. (Sec. 10.6) followed by TBA-Sulfur
cleanup (Sec. 10.2.).
7.1.26. Save the unused sample extract in the original tube with the remaining
volume clearly marked with initials and date.
SEDIMENT SAMPLE EXTRACTION FOR FENAMIPHOS AND ITS
METABOLITES
Extract as in 7.1 ROUTINE CHLORINATED/NITROGEN PHOSPHORUS
PESTICIDES and PCB's with the following exceptions:
7.2.1. Add surrogate spike mix for 5 mL final volume.
7.2.2. After K&D concentration, transfer the sample extract directly to a centrifuge
tube, rinse the concentrator tube two times with I mL, of methylene chloride and
once u ith I ml. of toluene, transferring the rinse to the centrifuge tube each
time. Be careful not to add more than I nil. of toluene, as toluene has a high
boiling point, and \v ill take a long time to concentrate.
7.2.3. Blow dow n with N-Kvap to 0.5 ml. Make up to 5 mL using toluene. There is no
need to add more toluene and blow clown more than once, as >ou would u ith
iso-octane.
7.2.4. If necessary do three gram Florisil column cleanup on 1 mL out of 5 mL of
original extract (see sec. 10.5) and make up to 1 mL in toluene.
7.2.5. Alternatively, same extract prepared for Pesticides analysis in 7.1 may be shared
for S-FEN.
SEDIMENT SAMPLE EXTRACTION FOR FLUSILAZOLE AND ITS
-------
Extract as in 7.1 ROUTINE CHLORINATED/NITROGEN PHOSPHORUS
PESTICIDES and PCB's with the following exceptions:
7.3.1. Add surrogate spike mix for 5 mL final volume.
7.3.2. After K&D concentration, transfer the sample extract directly to a centrifuge
tube, rinse the concentrator tube two times with I mL of methylene chloride and
transferring the rinse to the centrifuge tube each time.
7.3.3. Blow down with N-Evap to 1 ml. Make up to 5 mL with methylene chloride.
7.3.4. Do GPC and one gram Florisil column cleanup on 0.5 mL out of 5 mL of
original extract and make up to 0.5 mL in methylene chloride with 12.5 ul of 10
ug/ml TPP internal standard.
7.3.5. Alternatively, same extract prepared for Pesticides analysis in 7.1 may be shared
for S-Fluz analysis.
8. WASTE SAMPLE
This procedure is for .samples soluble in organic solvents:
8.1 Weigh 1,0g of sample into a centrifuge tube.
8.2 Weigh 1,0g Iso-Octane for blanks and lab fortified blanks into centrifuge tubes.
8.3 Add NPD/ECD surrogate spike mix to all samples (100 ul). Add required matrix spike
solution (check work order for specifics) to the Laboratory Fortified Blanks and Matrix
Spikes.
8.4 Dilute each sample to 10 mL with Iso-Octane. Cap tightly and vortex.
9 FILTER SAMPLES - FENTHION, MALATHION AND TEMEPHOS BY SOXHLET
EXTRACTION OF FILTER PAPER FOR ANALYSIS BY NPD.
9.1 Fill 500 mL round-bottom flask with 250 mL methylene chloride, set in a support ring,
then add four or five boiling chips to flask . Fit an extractor body on top of flask.
9.2 Fold the filter paper into quarters, then push the filter to the bottom of the extractor body
using forceps.
9.3 Spike at this point with the assigned spiking solution and volume.
9.4 Place the assembled extractor on the Rot-x-tract apparatus for 18 hours at 75°C.
9.5 After 18 hours, remove the extractor from the apparatus, rinsing all parts into the
extractor with methylene chloride. Tilt the extractor to empty its contents into the
attached 500 mL flask, remove the body from the flask and rinse the joint with methylene
chloride, catching the rinsate in the flask.
9.6 Transfer the extract to an assembled K&D apparatus, add fresh boiling chips and attach
a Snyder column.
GC-002-l.DOC
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9.7 Concentrate to 3 to 4 mL and transfer extract in to a pre-calibrated centrifuge tube with
methylene chloride and 1 mL of toluene.
9.8 N-blow down to 0.4 mL and bring to a final volume of 0.5 mL with toluene.
10. CLEANUP PROCEDURES
10.1. Cleanup procedures may not be necessary for a relatively clean sample matrix. If
particular circumstances demand the use of a cleanup procedure, select from the
following procedures as appropriate:
10.2. TETRABUTYLAMMONIUM - SULFITE (TBA-SULFUR) (used for sulfur cleanup)
10.2.1. Prepare a solution of tetrabutylammonium hydrogen sulfate by dissolving 3.39 g
of tetrabutylammonium hydrogen sulfate in 100 mL of deionized water. To
remove impurities, extract this solution three times with 20 mL portions of
hexane. Discard the hexane extracts. Add 25 g sodium sulfite to the water
solution. Store the resulting solution, which is saturated with sodium sulfite, in
an amber bottle with a Teflon-lined screw cap. Label date and initial. This
solution can be stored at room temperature for one month.
10.2.2. To remove sulfur from sample extract, transfer 2 mis of sample extract (in iso-
octane or hexane) to a 40 mL clear vial or a centrifuge tube with a Teflon-lined
screw cap. Add 1 mL of TBA - Sulfite reagent and 2 mL of 2-propanol. Cap
the vial and shake for 1 minute.
10.2.3. If the sample is colorless or if the initial color is unchanged, and if clear crystals
( precipitated sodium sulfite ) are observed, sufficient sodium sulfite is present.
If the precipitated sodium sulfite disappears, add more crystalline sodium sulfite
in approximately 100 mg portions until a solid residue remains after repeated
shaking.
10.2.4. Add 5 mL distilled water and shake for at least 1 minute. Allow the sample to
stand for 5-10 minutes and centrifuge. Transfer the top hexane layer to a 2 mL
GC vial or to a centrifuge tube for analysis.
10.3. GPC CLEANUP PROCEDURE
10.3.1. GPC Cleanup procedures are applied to all sediment samples, group AA water
samples and may be used for any sample if needed.
10.3.2. Column Maintenance
10.3.2.1.The column should be back-flushed between large sample sets (35-50
samples).
10.3.2.2. Reverse the flow of methylene chloride through the column and allow
it to run at 4 ml/min.
GC-002-l.DOC
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10.3.2.3. While the column is reversed, inject 1 mL tetrahydrofuran (THF), then
after five minutes, inject 1 mL toluene. Allow the column to back-
flush for another 30 min.
10.3.2.4.Return the column to its normal configuration and let flow run through
for 30 min.
10.3.3. Calibration of the column
10.3.3.1.Set up multichrom to collect data. The column is calibrated using a
254-nm detector. Use the GPC Calibration Solution (prepared in
section 4.8) for calibration. Inject 1 mL methylene chloride blank
followed by 1 mL GPC calibration mix onto column. Use the
following criteria for choosing dump time and collect time:
Peaks must be observed and should be symmetrical for all compounds
in the calibration solution;
Corn oil and phthalate peaks must exhibit > 85% resolution;
Phthalate and methoxychlor peaks must exhibit > 85% resolution;
Methoxychlor and perylene peaks must exhibit > 85% resolution ;
Perylene and sulfur peaks must not be saturated and must exhibit >90%
baseline resolution.
10.3.3.2.The collection window for ECD parameters should begin after 75% of
the bis-2-ethylhexyl phthalate peak has eluted and should end just
before the sulfur peak begins.
10.3.4. GPC Extract Cleanup
10.3.4.1.Set up fraction collector with proper time window to collect sample
extract and 50 mL tube with proper label to collect.
10.3.4.2.Start run sequence with a methylene chloride GPC blank, ECD-A GPC
spike (same spike level as in the LFB and matrix spikes, dilute spike in
methylene chloride) and followed by samples in the set. End GPC run
by injecting CH2C12 blank and corn oil.
10.3.4.3.Dirty samples, viscous samples which are difficult to concentrate and
dark colored samples need multiple injections of 1 mL extract ( 2 x 0.5
mL or 4 x 0.25 mL ).
10.3.4.4.Be sure to enter appropriate information in GPC log book.
10.3.4.5.For ECD add 1 mL of iso-octane and N-blow down to 1 ml. Solvent
exchange two more times by adding 1 mL iso-octane and N-blowing
down to 1 ml. If more than one injection is made for same sample,
then concentrate by K&D follow by N-blow down and solvent
exchange in the concentrator tube. Proceed to section 10.6 FOR ONE
GRAM FLORISIL CARTRIDGE CLEANUP.
GC-002-I.DOC
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10.3.4.6.If no ONE GRAM FLORISIL CARTRIDGE CLEANUP is required,
then N-blow down and make up to proper volume and solvent for
direct analysis.
10.4. ONE GRAM FLORISIL CARTRIDGE CLEAN UP
10.4.1. Clean vacuum manifold valves and needles with acetone.
10.4.2. For each sample place a properly labled one gram Florisil cartridge into the
vacuum manifold.
10.4.3. Wash each cartridge with 5 mL of hexane.
10.4.4. Apply and adjust vacuum if needed (vacuum is not usually needed), but do
not let the cartridges go to dryness.
10.4.5. Place a rack containing labeled 15 mL centrifuge tubes inside the manifold,
and replace the manifold top. Make sure that each cartridge position empties
into the appropriate centrifuge tube.
10.4.6. Transfer crude extract (approximately 1 ml) to the top frit of the appropriate
Florisil cartridge.
10.4.7. Rinse each tube with 3 mL of hexane-acetone (90:10) solution. Add rinsate to
cartridge. Repeat twice and finally rinse each cartridge twice with 1 mL of
hexane.
10.4.8. N-blow down to 0.8 mL and make up to 1 mL in iso-octane. The final
volume should result in a concentration equal to that of the extract initially
taken for clean up.
10.4.9. If sulfur clean up is required, proceed to "TBA-Sulfur clean up (Sec. 10.2)".
Transfer final extract to a labeled GC vial.
10.4.10. Each new lot of Florisil cartridges must be checked for acceptable
performance using the following procedure:
10.4.10.1. Place 1 mLofa 100 ng/ul of2,4,5-trichlorophenol, 0.5 mL of
ECD M1X-A-L1 and'
concentrate to 0.5 ml.
ECD M1X-A-L1 and 4 mL of hexane in a centrifuge tube and
10.4.10.2. Transfer this solution to the top of a hexane washed Florisil
cartridge with a proper 15 mL centrifuge tube to collect, and
follow steps 10.4.6-10.4.8. The final volume should be 2 mL in
iso-octane.
10.4.10.3. Analyze the resulting extract by GC/ECD. The recovery of each
analyte must be determined for evaluation and reporting
purposes.
10.4.10.4. The lot of Florisil cartridges is acceptable if all pesticides are
recovered at 80 - 110 %, if the recovery of trichlorophenol is
GC-002-l.DOC
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less than 5%, and if no peaks interfering with the target analytes
are detected.
10.5. THREE GRAM FLORISIL COLUMN CLEAN UP OF FENAMIPHOS AND ITS
METABOLITES
10.5.1. Pack a glass column with a plug of glass wool, 1 cm of N;i:SO„ 3 grams of
Florisil (prepared as in section 4.13 ), and 1 cm of granular Na:S04.
10.5.2. Wash column with 20 mL of 2.5% acetone - 97.5% benzene .
10.5.3. Transfer a portion of sample extract (in toluene) onto column.
10.5.4. Elute with 2x10 mL of 2.5% acetone - 97.5% benzene. Collect into a 50 mL
labeled culture tube. For samples, retain this eluant; if sample is highly
contaminated, this fraction must be concentrated and analyzed separately.
10.5.5. Elute with 100 mL of 90% acetone - 10% benzene into a clean, 500 mL K&D
flask and concentrate to 2-4 mL on K&D apparatus.
10.5.6. Transfer the extract to a 10-15 mL centrifuge tube with methylene chloride and
with 1 mL of toluene. N-blow down to 0.5 mL and make up to 1 mL with
toluene.
10.5.7. If sample is suspected to be highly contaminated, a second 100 mL fraction with
90% acetone - 10% benzene should be collected into a 125 mL Erlenmeyer flask
and stored with the first fraction for later analysis.
10.5.8. CAUTION: Validation with 10 ng/ul FEN-MET-M1X-STD in toluene gave
quantitative recovery. With low concentrations this method works well. For
high levels, all the three fractions should be analyzed.
10.6. SULFURIC ACID CLEAN UP (USED FOR SAMPLES BEING ANALYZED FOR
THE ACID RESISTANT PESTICIDES)
NOTE: This clean up will destroy some pesticides. Do sulfuric acid clean up on part of
the sample. DO NOT TREAT ENTIRE SAMPLE WITH ACID!!!
10.6.1. Add 8 mL of concentrated sulfuric acid to 2 mL of sample extract (in iso-
octane) in a screw-top culture tube. Be sure the top of the tube has no chips or
cracks.
10.6.2. Shake for 30 seconds, allow to settle for five minutes and then centrifuge for
five minutes.
10.6.3. If the bottom layer is colored, then transfer the top layer to a tube containing 8
mL of fresh sulfuric acid and repeat step 10.6.2. May need to repeat this step
until a colorless acid layer is observed.
10.6.4. Transfer the supernatant into a clean centrifuge tube. Extreme care must be
exercised at this point. All of the sulfuric acid layer must be avoided during
GC-002-l.DOC
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transfer as this layer will destroy the GC. Processing the extract through lg
Florisil column (Sec. 10.4) will eliminate this danger.
10.6.5. All sediment extracts from concentrated sulfuric acid clean up with out GPC
need TBA-SULFUR clean up (Sec. 10.2).
11. SAMPLE ANALYSIS PROCEDURE
Reference applicable analysis Sop's, GC-010 and GC-011.
12. QUALITY CONTROL
12.1. Matrix spikes and laboratory fortified blanks are used to evaluate the accuracy and
precision of the method.
12.2. A reagent water/sediment blank, two duplicate matrix spikes, and one lab fortified
reagent water blank should be prepared with every sample set (not to exceed 20
samples). If there is not sufficient sample to run duplicate matrix spikes, run one matrix
spike and duplicate lab fortified reagent water blanks, or one lab fortified blank and
duplicate samples.
12.3. See QA/QC SOP GC-001.
13. SAFETY/HAZARDOUS WASTE MANAGEMENT
See Safety SOP OG-OOl.
14. REFERENCES
14.1. EPA Method 608: Code of Federal Regulations, Title 40, Part 136\ US Government
Printing Office, Washington, DC, July 1993.
14.2. EPA Methods 614. 617 and 619: Methods for the Determination ofNonconventional
Pesticides in Municipal and Industrial Wastewater, USEPA Office of Water,
Washington, DC, 8/93.
14.3. EPA Method 3500. 3510. 3540. 3550. 3580. 3620. 3640. 3660, 3665: Test Methods for
Evaluating Solid Wastes, Physical/Chemical Methods, SW-846; 3rd edition (9/86), with
Final Updates I (7/92), II (9/94), IIA (9/93) and IIB (1/95); USEPA Office of Solid
Waste and Emergency Response, Washington, DC
GC-002-1 DOC
-------
Revision Date: 04-10-98
Author: Adrian Niculescu, Mike Acton, Lih-Ji-Wang /Adrian Niculescu
GC-011-3
ANALYSIS OF ORGANOCHLORINE PESTICIDES AND PCBs IN WATER,
SOIL/SEDIMENT, AND WASTE EXTRACTS BY GAS CHROMATOGRAPHY
WITH ELECTRON CAPTURE DETECTION ( GC/ECD).
1. SCOPE AND APPLICATION
1.1. This method is applicable to the determination of 36 organochlorinated pesticides and 7
arochlors in water, sediment, and waste as listed in Table 3. Method Detection Limits
and Practical Quantitation Limits yielded by this method are also provided in Table 3.
1.2. This method is built on EPA methods 608,617,8081.
2. SUMMARY OF THE METHOD
2.1. Water, soil/sediment or waste samples are extracted using the appropriate procedures
listed in the Preparation SOPs. The extract is analyzed using a Gas Chromatograph (GC)
equipped with two capillary GC columns and two Electron Capture Detectors (ECDs) to
provide confirmatory analyses for all positive hits.
3. APPARATUS AND EQUIPMENT
3.1. Gas Chromatograph: Hewlett Packard 5890 Series II, Series II Plus, or 6890 capable of
four step temperature programming, with dual electron capture detectors, dual capillary
split/splitless injectors and a dual HP 7673 Automatic Sampler. The GC and GC
Automatic Sampler are set at the operating parameters shown in Table 1 and Table 2
( See APPENDIX / Table 1 & 2 ).
3.2. The primary analytical column is a DB-5, J & W fused silica capillary, 30 m x 0.32 mm
x 0.25 um or similar column.
3.3. The confirmatory column is a DB-608, J & W fused silica capillary, 30 m x 0.32 mm x
0.52 um or similar column.
3.4. Data system
3.4.1. A computer system is interfaced to the Chromatograph that allows the
continuous acquisition and storage on machine-readable media of all
chromatographic measurements obtained throughout the duration of the
chromatographic run sequence program.
3.4.2. This system currently uses the VAX MULTICHROME software from FISONS
INSTRUMENTS which acquires, and allows the processing and reporting of,
the chromatographic data.
3.4.3. For reporting data, the system currently uses: DEP LIMS and DEP QC
CALCULATOR softwares.
-------
4.4.1. These solutions are used when fortifying sample matrix spikes or lab fortified
blanks at extraction. These fortified samples are used to verify the accuracy and
precision of the sample preparation and analysis.
4.4.2. Spike solutions are prepared by diluting stock or intermediate standards with
acetone. Concentrations of the parameters in these solutions are listed in Table
4.
4.4.3. Freshly prepared spike solutions are checked vs. valid working standards and
the acceptance criterion is +/- 10 % difference.
4.5. Quality Control Check Standards (QCS)
4.5.1. Quality Control Check Standards are prepared from a source other than
calibration standards that are certified and traceable. These standards are used to
check the integrity of the calibration standards.
5. SAMPLE COLLECTION, PRESERVATION, AND HANDLING
5.1. Samples must be collected in glass containers.
5.2. All samples must be iced or refrigerated at 4 degree C from time of collection untill
extraction.
5.3. All water samples must be extracted within 7 days of collection and completly analyzed
within 40 days of extraction.
5.4. All sediment and waste samples must be extracted within 14 days of collection and
completly analyzed within 40 days of extraction.
6. SAMPLE PREPARATION PROCEDURE
6.1. See: ISOLATION OF ORGANOHALIDE PESTICIDES AND PCBs FROM WATER,
SEDIMENT, AND WASTE FOR SUBSEQUENT ANALYSIS BY
GC/ECD.(Preparation SOP GC-021-1).
7. GENERAL DESCRIPTION OF GC/ECD ANALYSIS
7.1. Pre-Run GC Maintenance
7.1.1. Before starting an analysis run sequence, an initial checking and maintenance of
the instrument has to be performed ( see 9.1 this SOP )
7.2. Summary of GC/ECD Analysis
7.2.1. The analysis of samples is accomplished by using two dissimilar fused silica
capillary columns, usually a DB-5 and a DB-608 or similar column (usually
0.32mm ID/30m/0.25-0.50 um).
7.2.2. Analysis is accomplish in two steps: identification of positives (1) and
quantification of the positives (2).
7.2.3. First step requires to meet following QA/QC criteria:
• Use of an updated single or multipoint calibration ( updated Retention Times
and Response Factors)
• Stable retention time windows ( all calibration check standards within the
calibration windows)
• Recoveries for surrogates and spikes within the control limits
• Calibration check standard responses in both columns not bellow 50% of initial
calibration
• Decomposition of Endrin and DDTin both column not more then 50%
-------
of the same matrix has been analyzed, calculate the average percent recovery (p
) and standard deviation of the percent recovery for each of the surrogates, (3 )
for a given matrix, calculate the upper and lower control limit for method
performance for each surrogate standard as follows:
7.2.10. Upper Control Limit (UCL) = p+ 3s
7.2.11. Lower Control Limit (LCL) = p- 3s
7.2.12. For Surrogates a single point calibration is used at the level spiked, and the
results are expressed directly in % recovery. The acceptance criteria for
surrogates are : Tetrachloro-m-xylene 27 - 81 % (water), 20 - 110%
(sediment/soil) and 27-81 (SFWMD group A A); Decachlorobiphenyl 56 - 134
% (water), 44-146 % (sediment/ soil) and 61-145 (SFWMD group AA). If, in
both columns, the acceptance criteria for DCB fails, check TMX . If TMX also
failed, the sample has to be reextracted and reanalyzed. If sample exceeded the
holding time for extraction, the reextraction is not required and the found hits
have to be qualified as estimated with the following comment entered in the
Sample Report: "Estimated values for are due to surrogate recovery for
TMX/DCB out of control limits".
7.2.13. The ECD response for singlecomponent and multicomponent analytes must be
within the calibration range in order for a quantitative measurement to be made.
The sample extract must be diluted if the ECD response exceeds the calibration
range. Quantitation must be performed for both GC columns and the primary
channel value reported into the L1MS.
7.2.14. Absolute Retention times ( Rts) are used for the identification of targets. The
absolute retention time window is assessed during initial calibration as +/- 0.05
minute of the mean RT of the analyte.
7.2.15. Calibration curves with single point calibration created for single component
analytes (ECD B and ECD C) are run for screening purpose. If there are
identified hits at the PQL level or higher which belong to these mixtures, the
samples have to be rerun and reanalyzed using a multipoint calibration curve.
7.3. Instrument Initial Calibration
7.3.1. Quantitation of every hit at PQL or higher level for single component analytes
has to be accomplished by using the linear range of at least 3 level calibration
curve.
7.3.2. To initially calibrate using external standard technique, analyze three to five
concentration levels of calibration standards ( ECD A, ECD B, ECD C), by
injecting 0.5 or 1.0 uL of each working standard. The multiple component
parameters ( Toxaphene, Arochlors, Chlordane ) may be quatified using a
single-point calibration.
7.3.3. The system is considered in initial linear calibration, and analysis of the samples
may proceed if the Relative Standard Deviation (%RSD) for the analyte
response factors (using peak area calculation) is less than or equal to 15% or a
coefficient of correlation not lower than 0.995.
7.4. Continuing Calibration
7.4.1. After initial calibration, the GC/ECD calibration is checked on a continuing
basis (every 7-10 samples ) by using a calibration check, usually ECD A level 4
-------
fulfilled and the peak area integration was correctly done. If not, the integration
has to be re-done by choosing a new set of integration parameters or by manual
integration. Additionally, the analyst must complete the calculation to determine
the concentration of the analyte in the sample. This is done as follows:
• Cample (ug/kg) = (cx) x (vextract) x (DFy(Wsampie) for sediment
and waste
• Csample (ug/L ) = (Cx) x (Vextract) x (DF)/(Vsample) for water
sample
• where:
• Cx the concentration, in ug/L, of the analyte in the
sample extract
• Vextract- the volume of the extract, in mL (usually 10 mL)
• DF - the appropriate dilution factor
• ^sample" for sediment is the dry weight of the sample that was
extracted, and for waste is weight of the sample taken for extraction
expressed in grams.
• Vsample - is the volume of the water sample taken in extraction,
expressed in mis (usually 1000 ml )
7.7. Report results in DEP LIMS.
7.7.1. Report QA/QC results, MDL s and positives using QC Calculator (see 5.8.
Reporting in QC Calculator).
8. QUALITY CONTROL
8.1. A QA/QC set of samples for an extraction batch (not to exceed 20 samples) should
consist of one instrument blank, one reagent extraction blank, one laboratory fortified
blank and duplicate sample matrix spikes (see Preparation SOP).
Recoveries must be in the range of 50-150% ( for endrin 50-170%) acceptance criteria.
These statuary limits are periodically checked, at least once per year, but not sooner than
untill 20 routine QC checks will be available for calculation. If the recovery of any one
of the two sample matrix spikes is out of accepted values, the batch of samples has to be
re-extracted provided that samples are not expired and the problem occurring is not due
to the matrix interference. If samples are expired, then the result is qualified as
estimated for those parameters.
8 2. The recoveries of matrix spikes components are calculated, recorded and reported in a
QA/QC report. After at least 20 spikes for the same matrix have been analyzed, the
average percent recovery ( P = method accuracy) and the standard deviation (s) can be
calculated. The Accuracy Control Limit is expressed as a percent recover)' interval from
P - 3s to P + 3s. The new calculated Control Limit is supposed not to exceed the statuary
control limits. If so, the occurrence has to be recorded and corrective action has to be
-------
p,p' peak area by the sum of the DDD-p,p' and DDT-p,p' peak areas. The sum
of the two values should not exceed 30%, or 20% individually. If so, change the
liner on the injector with the high decomposition and check again the
decomposition. If again it is high, the GC column must be cut approximately
four inches from the injector end (see column cutting below for further details),
and the decomposition must be checked. If again it is bad, the corresponding
column must be cut, and the decomposition rechecked. If still it is bad, notify
your supervisor.
9.1.9. Once the decomposition is checked, fill two vials with isooctane and place them
in the autosampler tray in position 1 and 51. Start a preventative maintenance
run by typing on the GC integrator, 'load' 'sequence' 'bake2' 'enter'. Then
press 'sequence' 'start'.
9.1.10. Begin to pour out the samples. First label each GC vial with the sample number
of on the tube. If the set is a soil set, or the sample has less than 2mL of
volume, place an insert into the GC vial. Fill the vial (or insert) to about half
volume. Cap the vial. Continue through the set. Mark the new volumes of the
samples on the tubes and place them back in the refrigerator when you are done.
9.1.11. Plan which standards you need to use and pour them out in the same manner.
Inserts are usually not used. See the attached run sequence for most common
standards used. If the PCB's are needed, individual PCB's at level 4 should also
be poured out. Standards should be tightly capped and placed back in the
refrigerator when you are done.
9.1.12. Login to Multichrom. Edit the sample run on the front injector. (This is usually
an even number) Type'$er' 'enter''your channel number''enter'. Type the
sequence name, usually 617. Press enter. You will now be given the Header
Page Parameters.
9.1.13. Change the analysis name to the current date using this format 010197, for
instance. Place an 'A' after the date if this is the first run of the day. If it is the
second, place a 'B', and so on.
9.1.14. Change the method name to the method you are using. Usually this is 617, and
need not be changed.
9.1.15. Change the analyst name to your name.
9.1.16. Press'page down'. This puts you to the first sample. Note in the upper right
hand comer it will list 'sample 1 (of 40)' for instance. Now press 'exit' 'd'
'enter'. Type'2-40' in this case. Press'enter'twice (for all samples). This
will delete all samples in the run sequence except the first one, where you will
begin to edit your run sequence.
9.1.17. Isooctane should be placed as the first two samples. The next sample should be
the appropriate level and standard used to spike the QC. This information is
found on the extraction report. Following this standard should come all QC
samples, including any GPC spikes (if this were a set of soils), LFBs, and
Matrix spikes. After the QC set, place the standards, at their appropriate levels,
to be used, ECD A L4, ENDT L3, ECD B L3, ECD QC STANDARD, CHLD
L4, TOX L5, CHLDTOX QC STD, PCB 1016+1260 L4, PCB QC STD. Next
place the extraction blank, followed by the first six samples. Following this
comes the ECD A calibration set, then the next seven samples. A Continuing
Calibration Check std at PQL (or 2x PQL) level usually ECD A L4 is placed
after every seven samples. After typing in all the samples, place the same
standards which are bracketing first set of samples at the same level at the end
-------
Cool the machine. This is done by typing 'load' 'method' 'cool'
'enter' on the GC integrator.
Remove the both injector towers and place them on the posts near the
top-back of the machine.
Using the tool, remove the nut located under the gas lines on the
injectors. The nut and attachment will lift up, revealing the liner
inside.
Remove the liner using a set of tweezers. Grasp the side of the liner
and using only enough force to move the liner, pull it straight up and
out of the injection port. Continuing to use the tweezers, lay the liner
aside.
Being careful not to touch the new liner (we use single tapered liners)
in excess, place and o-ring seal about a quarter of the way down the top
of the liner, (the top of the liner is the end without the taper) Now,
insert the liner into the injection port, tapered end first.
Replace the nut and tighten securely, but not in excess. Use care not to
cross thread the nut.
Remove the nut on top of the injection port, above the gas lines, (it is
usually green) This will reveal the septa.
Remove and replace the septa, using a solid septa.
Replace the nut, and tighten securely, usually this is finger tight, with
about a quarter turn more with the wrench.
Repeat for the next injection port.
Replace the injection towers and check to be sure the green light
appears on the tower, indicating you have replaced it properly.
Place used liners in beaker to be cleaned. Throw away used septa.
Throw away cracked or broken liners.
Record the changes in the Maintenance Log Book located under the
GC.
9.1.32. How to cut columns
Cool the machine down. This is done by typing 'load' 'method' 'cool'
'enter' on the GC integrator.
Open the oven door.
Using a quarter inch wrench, remove the nut connecting the column to
the injection port.
Slide the column through the nut, exposing the ferrule. Remove the
ferrule by pulling on it, or by cutting it off using the ceramic square
cutter located inside the oven. If the column will not slide through the
nut, cut the nut off, and dig the ferrule out of the nut.
Slide the nut back on the column.
Slide a 0.5mm ID ferrule on the column with the flat side of the ferrule
going on first. In this way the tapered end should be closest to the
exposed end of the column.
Slide the column through the nut-ferrule assembly about ten inches.
Cut about four inches off the column using the ceramic square.
Inspect the cut using a magnifying glass. The cut should be straight,
with no jagged edges. If it is not, cut the column again, just below the
original cut until it is good.
To cut the column, hold the column in one hand, the cutter in the other,
and score the column with the cutter. Use your index finger to break
off the scored piece.
Measure the column from the end of the ferrule. Move the column so
that this distance is 4mm. (for most HP instruments) Mark the column
at the back of the nut using a felt pen.
-------
number of the first sample you want to overlay. This is done by
pressing 'TAB' and arrowing over using the arrow keys to the analysis
name (if it is not yours) or sample number. Type in the new sample
number. Press 'SPACE BAR' until you see no more characters or
numbers. Press 'enter'. Do the same for the rest of the samples you
want to overlay. When you have finished entering the samples, press
'enter' four times. This will be referred to as isometric plot type r.
9.2.1.7. Visually inspect the heights of the two peaks in the surrogate standard
to the heights of the same two peaks in all the samples. If either of the
two peaks is missing or obviously low, quantify them with your
surrogate calibration file and print out the analysis report for the
sample in question to further asses the surrogate recoveries. If the
surrogate recovery is out of our acceptance range, immediately report
this to you your supervisor, and ask the organic prep supervisor to
reextract the sample. If the peaks have shifted greatly in all the
samples in either channel, it is possible you will have to rerun the
sample(s), and you should consult with your supervisor. Check all the
samples in this manner.
9.2.1.8. While checking the surrogates, you should also be looking for any
'large' or 'offscale' peaks. Samples containing such peaks should be
checked (using isometric plot type r) versus the other standards to see if
they are, or contain, any peaks of interest. If so, you should check the
other channel, and if it seems remotely possible that the peak is of
interest, the sample(s) should be diluted and reshot with the appropriate
standards.
9.2.2. Initializing standards for Calibration
• 9.2.2.1. Type in'$AE' 'your channel number' 'your analysis name' 'enter'.
This brings you to the Edit Analysis Header Parameters page, referred
to as analysis edit. Go to the first standard before the QC set by typing
'exit' 's' 'sample number' 'enter'. Arrow down to sample type.
Change this to 'standard' (usually by pressing select five times). Now
arrow down to RT update. Change this value to 'initialize' (usually by
pressing select once). Arrow down and enter the appropriate
Calibration level ID (usually this is seen in the sample name). Arrow
down once more and change the RF update to 'initialize' (usually by
pressing select once). This is called initialize.
9.2.2.2. Now go to the same standard at the end of the QC and change its
sample type to standard as above. Arrow down to the RT update and
change the value to read 'average'. Arrow down once to Calibration
level id and enter the level of the standard (this is the same as the
previous standard, and should be seen in the sample name). Arrow
down once again to RF update and change the value to 'average'. This
is called average.
9.2.2.3. You will repeat step one for each of the standards located at in front of
the samples and step two for each of the standards located after the
samples. The exceptions are the actual standards bracketing the QC
set, and all standards in the three point calibration curve and their
corresponding check standards, (see below) This sets up which
-------
9.2.3.9. You should repeat steps 1-7 for the next channel.
9.2.4. Updating Calibration Files
9.2.4.1. To update a calibration file type'$FCC' 'your channel number' 'enter'.
This will bring you to a list of all calibration files for the channel. By
using the codes below, arrow down until you come to the most recent
file for the calibration you are updating. Press 'select' 'do'. This will
bring you to a new page allowing you to change the channel number
and calibration name. Arrow over to the calibration name and enter the
new name using the instructions below. When done press 'enter' three
times.
9.2.4.2. Calibration files are named as follows: C10A0101. In this example,
'c' is for channel, '10' is the channel number, 'A' is the standard
mixture, '0101' is the month and day of the analysis. Examples for
most calibration files are below. Channel 10 will be used for the
channel number, and 0101 for the month and day. Further clarification
will be provided if necessary. This will be referred to as Calibration
name:
• ECD A Mix = clOaOlOl
• ECD B Mix = clObOlOl
• Endrin DDT-p,p'Mix = endtOlOl
• Surrogate = surrOlOl
• Chlordane & Toxaphene Mix = cltxO 101
• PCB 1016 and PCB 1260 Mix = 10600101
• Chlordane Technical = chldO 101
• T oxaphene = toxaO101
• PCB 1221 = 12210101 (likewise for PCB 1016, 1232, 1242,
1248, 1254, 1260)
ECD F Mix = clOfOlOl
PCB Congeners Mix = congOlOl
To edit a calibration file type in the 'SEC' 'channel number' 'SPACE
BAR' 'calibration name' 'enter'. This will bring you to the calibration
header page and will be called edit calibration.
Enter the appropriate Calibration Title. This is usually the name of the
calibration, for instance, ECD A Mix Calibration File.
ECD uses an external calibration file mode, and two examples are
given. One is for a single point calibration, the other is for a three
point calibration. It should be noted that only the Calibration title and
the corresponding peak information will be the only difference in the
files. All other values should be the same.
9.2.4.3.
9.2.4.4.
9.2.4.5.
-------
9.2.5.4. When you have finished, press 'e' 'o' 'p'. Scroll through the
chromatogram using 'PAGE DOWN' to be sure all peaks are selected.
Look for obvious errors.
9.2.5.5. When through, press 'exit' twice, and press 'enter'. This will save the
updated retention times in your calibration file.
9.2.5.6. IMPORTANT: Be certain you have chosen the right peak. They are
usually not shifted much, and are usually shifted to an earlier retention
time. If you have any question over which peak is which, ask your
supervisor.
9.2.5.7. Repeat steps 1-4 for all calibration files in your run.
9.2.5.8. Exit from analysis edit.
9.2.6. Calibrating
9.2.6.1. Go to analysis edit. Enter the calibration name for the calibration file
you wish to calibrate and exit analysis edit.
9.2.6.2. Type in 'SAC' 'channel number' 'enter'. Enter your analysis file name
and press enter. Enter the sample number of the standard you want to
calibrate that is 'initialized' and press enter twice.
9.2.6.3. Do the same, but enter the sample number for the standard of the
calibration that is 'averaged'.
9.2.6.4. Type in 'SAQ' 'channel number' 'enter'. Enter you analysis file name
and press enter. Enter the sample number of the standard you
calibrated first and press enter twice. Type in 'SAR', and follow the
same procedure.
9.2.6.5. Do the same for the standard that was averaged (calibrated second).
This quantifies and prints out a report containing information from the
calibration.
9.2.6.6. Follow the same procedure for all calibration files you have. An
example of the order most commonly used is listed below.
• Surrogate
• Endrin
• ECD B Mix
9.2.6.7. For you three point calibration, calibrate in the same manner using the
'initialized' standard first, followed by the next two levels.
CLTX
PCB 1060
• ECD A Mix
-------
same peak in the ECD A Mix calibration file. Change the count value
to '2' for this peak at this level.
9.2.7.2. Do the same for second surrogate peak (DCB). It will be the last peak
of interest in the file.
9.2.7.3. Repeat steps 1-2 for the other channel.
9.2.7.4. Go to edit calibration for the ECD A Mix. Find the peak name
'Endrin'. Type in the RT EXP, RF slope, and change the count, as in 1
above, using the Endrin calibration file. Do the same for the peak
named 'Alpha Chlordane' using the same Endrin calibration file.
9.2.7.5. Repeat step 4 for the other channel.
9.2.8. Quantifying
9.2.8.1. Go to analysis edit. Type in the calibration file you wish to quantify
with in calibration name. Exit out of analysis edit.
9.2.8.2. Type 'SAQ' 'channel number' 'enter'. Enter you analysis name and
press enter. Enter for sample a value of'0'. This will quantify all
samples in the file with the calibration file you typed in ' 1' above.
9.2.8.3. For all single point calibrations, type '$AR' 'channel number' 'enter'.
Enter your analysis file and press enter. Enter '0' again for all samples.
For your three point calibration, replace the $AR command with SAX.
This will print out a combined report, displaying a chromatogram
with the peak information.
9.2.8.4. To size the window for the chromatogram in the combined report, goo
edit method. ('Sem' 'channel number' 'SPACE BAR' 'method name'
'enter').
9.2.8.5. Go to page 6 ('exit' '6' 'enter'). This will be Plot Parameters.
9.2.8.6. Change the Y scaling minimum height to about 30-35, and the
maximum height to a value between 300-500.
9.2.8.7. Change the Plot timed window start time to one minute before your
earliest eluting peak from all calibration files (usually this will be from
the Surrogate file or ECD B Mix file). Change the End time to one
minute after DCB elutes (from the Surrogate calibration file).
9.2.8.8. Exit out. The goal is to show all the peaks of interest in the
chromatogram displayed in the combined report. If you size it too big,
nothing can be seen, but to small doesn't display enough information.
Ideally you will select values that will work for all samples, Sometimes
this is not the case, and you must resize the chromatogram for the
samples in which your original values do not work.
9.2.8.9. Repeat steps 1-3 for the other channel.
9.2.8.10.Once all the samples have been quantified and printed out, sort them by
sample and calibration. Usually this is done by separating all reports
by channel and calibration, then combining each channel of the same
sample and calibration, then combining each sample with the other
calibration files of the same sample. An example is below.
-------
9.3.6. Check the recovery of the surrogates in the sample. If DCB is out of the
acceptance limits check TMX. If this is also out rerun the sample. If this does
not fix the problem, the sample has to be reextracted. If the sample has expired,
qualify all positives found as estimated and write on the sample report following
comment: " Estimated value for is ( are) due to surrogate recovery failing
acceptance criteria".
9.3.7. Check the recovery of the component in the calibration check standards
immediately before and after the sample. If the recovery in any of the check
standards for the component believed to be positive is out of +/-15% of the
initial calibration, rerun the sample. This must be checked in both channels. If
the sample has expired, qualify the results as estimated ( for values higher than
PQL only). Write in the sample report a comment to explain the estimation.
9.3.8. Check to see if the amount is below your MDL. If so, it is important to note in
some cases the positive is still reported with the appropriate qualifier (T).
9.3.9. Check if the amount is below your PQL but above MDL. If so, report it with
the appropriate qualifier (I).
9.3.10. Report the positive as the average of the two columns. Use the appropriate
formula given in paragraph 6.6.2.
9.3.11. Qualifiers commonly used for reporting positives are listed below. When you
are in question of which to use, consult with your supervisor.
• I value reported is less than practical Quantitation limit.
• U Material was analyzed for but not detected. The value reported
is the minimum detection limit.
• J estimated value ( when reporting estimated value that value
has to be accompanied by a comment has to be used to explain the
reason for estimation ).
• T value reported is less than method detection limit. Report the
value found followed by T.
• N presumptive evidence of presence ( whenever there are
suspicions that a analyte may be present but there are not strong
enough evidences to assess it as positive). Has to be followed by a
comment explaining the reason for presumptive evidence.
9.3.12. Qualifiers (listed below) should be placed next to the component on the analysis
report.
• PC positive confirmed, for the components with right retention
time and matching amount (+/- 30 % ) in both channels.
• NPBL not positive bellow the detection limit.
• NPC not confirmed in confirmatory column (is not listed in the
confirmation channel report or is dismissed for a reason which is
specified).
• NPCB not confirmed by blank (if that component was reported in
the blank report, to be accepted as hit the amount in the sample has to
be 5 times higher than in the blank). Adjust MDL to the smallest
amount found in the two channels if this is higher than actual MDL.
V NPCRT not confirmed by retention time (if the retention time of that
analyte is still into the window but is badly shifted toward one of the
window extremes, and this shift is not confirmed by surrogates
retention times or already assessed hits).
-------
Calibration Check Standards Reports for ECD A
ECD A Level 3 ( Check Standard) Reports
ECD B Calibration Check Standard Reports
Chlordane Calibration Check Standard Reports
Toxaphene Calibration Check Standard Reports
PCB Calibration Check Standard Reports
QC Standard Reports (if single level calibration was used)
QC Samples Reports ( LFBs and Matrix Spikes)
GPC Spike Report (if any)
9.4.5. Collect all the injection reports for the instrument blank, each extraction blank
and each sample in the following manner: (primary channel report followed by
confirmatory channel report for each calibration set)
• ECD A Reports (including the Chromatogram, combined report using
SAX command)
• ECD B Reports
• Chlordane Reports
• Toxaphene Reports
• PCBs Reports
9.4.6. Put together for all the reports from Step 4 in a numerical order according to
their sample ID. On top of them put the previously filled Analysis Summary
Report.
9.4.7. Gather all documentation and the original Job folders in a Manila Folder and
bind it using a rubber band.
9.5. Reporting in QC-Calculator
9.5.1. Select instrument/method from the Analytical Setup screen. Usually you will
select GC Pesticides-High or GC Pesticides-Low.
9.5.2. Go to 'File' 'Convert Instrument File'
9.5.3. Select either GC-High or GC-Low and press 'enter'.
9.5.4. Give a new file name for your raw data. Usually this is your analysis file name.
For instance: Analysis file 010197a would become 01017a09 or 01017a 10.
9.5.5. Go to 'File' 'Initiate'. This brings you to the Data Initiation screen.
9.5.6. Enter the appropriate information in the boxes provided and press 'ok'. It is
important to note for the number of samples this is the number of samples plus
-------
9.5.23. Unhighlight everything by double clicking the right mouse button on the 'LIMS
Test ID button'.
9.5.24. Highlight all LFBs for the set. Press the'Sample Matrix'button. Choose S-
LFB or W-LFB depending on whether the set is soils or waters. Press 'ok'.
9.5.25. Unhighlight everything as in step 23 above.
9.5.26. If the set is a water set, highlight the LFBs and Matrix Spikes. Press the 'Spike
Factor' button. Change the value to match the value listed in the corresponding
'Dilution Factor' column. Unhighlight everything as in step 21 above and
proceed.
9.5.27. If you have any positives in your set of samples, highlight the sample, select the
component and enter the raw data. Repeat for all the positives.
9.5.28. Go to'Calculate'. Press'Begin'.
9.5.29. Uncheck 'SRM Recoveries' and 'Mean and Precision for Replicates'. Check
'Retain upload status for new QC rows'. Press 'ok'.
9.5.30. Go to 'File' 'Print' 'SPK/SPKRPD Components (choice 8). This will bring you
to the Choose Components screen.
9.5.31. Go to'Options'. Choose'Create LIMS upload by upload flag'.
9.5.32. Record this number for later use and press 'ok'.
9.5.33. Highlight all components in your spike mix. Press'ok'.
9.5.34. Click 'ok' to print.
9.5.35. Go to 'File' 'exit'. Choose 'yes' when prompted to save. Press 'save'.
9.5.36. Login to DEP LIMS.
9.5.37. Go to 'Laboratory' 'Technical' 'QC' 'UpLoad'. While in Upload window, go to
'File' 'Open'. Enter the upload number from step 31 above. Once file opened,
go to 'Do' 'Upload'.
9.5.38. Type 'N' for authorize results for uploaded samples.
9.5.39. Type 'Y' for first time data set uploaded.
10. SAFETY
10.1. Lab clothing
10.1.1. Lab coats and safety eyeglasses must be worn at all times when in any
laboratory.
10.1.2. Use gloves when handling samples, standards, or solvents, or when washing
glassware.
10.2. Chemicals involved
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12. APPENDIX
Table 1 GC OPERATING PARAMETERS FOR GC/ECD ANALYSIS
GC PARAMETER
SETTING
GC PARAMETER
SETTING
Temperature 1
80 degree C
Injector Temperature
250 degree C
Time 1
1 minute
Detector Temperature
325 degree C
Ramp 1
30 degree C per minute
Carrier Gas
Helium
Temperature 2
190 degree C
Column Head Pressure
18/10 psi
Time 2
0 minute
Total Flow Rate
36 mL per minute
Ramp 2
3.6 degree C per minute
Septum Purge Flow
Rate
4 mL per minute
Temperature 3
250 degree C
Make up Gas
Nitrogen
Time 3
2.67minutes
Make up Gas Flow Rate
55 mL per minute
Ramp 3
15 degree C per minute
Injection Mode
Splitless for 1 minute
Temperature 4
280 degree C
Injection Volume
0.5 uL/1.0 uL
Time 4
3 minutes
R T Window
0.08/0.1 minute
(NOTE: The operating parameters for both columns are the same).
TABLE 2 GC AUTOSAMPLER OPERATING PARAMETERS FOR GC/ECD ANALYSIS
Autosampler Parameter
Setting
Autosampler Parameter
Setting
Inj/Bottle
1
Volume
1/2
First Bottle
1
# of Solvent A washes
6 (Acetone)
Last Bottle
100
# of solvent B washes
6 (Iso-Octane)
# of Sample washes
2
Priority Sample (l=Yes)
No
# of Pumps
6
Capillary On-Column
(l=Yes)
No
Viscosity
1
TABLE 3 RETENTION TIMES, AND REPORTED MDLs AND PQLs FOR GC/ECD ANALYTES
The listed MDLs and PQLs are approximate and may change with time and matrix type.
Components
WATER
WATER
SOIL
SOIL
WASTE
WASTE
COMPONE
NT
RT DB-
608
R T DB-5
MDL
PQL
MDL
PQL
MDL
PQL
minute
minute
ug/L
ug/L
ug/kg
ug/kg
ug/kg
ug/kg
aldrin
7 53
10.88
0010
0 050
0 40
1 7
10
50
alplia-BHC
1032
7.73
0.010
0 050
0 40
1.7
10
50
beta-BHC
8.65
8 18
0.020
0 10
0.70
33
20
100
gamma-
BHC
8 47
8 33
0010
0 050
0 40
1.7
10
50
delta-BHC
9 86
8.33
0010
0.050
0.40
1.7
10
50
benlluialin
7.11
8 77
0 020
0 10
0 70
3.3
20
100
carbophcnot
hion
19.90
7 27
0.030
0 20
1 0
66
30
200
chlordanc
technical
0 10
1 0
50
33
100
1000
alpha-
chlordane
13 44
13.28
0010
0 050
0.40
1.7
10
50
gamma-
chlordane
16 42
12 73
0.010
0 050
0 40
1 7
10
50
chlorobenzil
ate
19 90
15 13
0.050
0 40
-
-
50
400
chlorothalon
il
12 18
8 85
0 020
0 20
0 70
66
20
200
-------
Methoxychlor
40.000
400
200
100
40
20
2,000
"CD B MIXTURE
^.arbophenothion
10,000
200
100
20
2,000
^¦lorobcnzilate
20,000
400
200
40
4,000
^Vlorothalonil
10,000
200
100
20
2,000
"Cypermethrin
10,000
200
100
20
2,000
Dicofol
20,000
400
200
40
4,000
lsodrin
10,000
200
100
20
2,000
Mirex
10,000
200
100
20
2,000
Oxadiazon
10,000
200
100
20
2,000
Pentachloronitrobenzene
5,000
100
50
10
1,000
Pendimethalin
10,000
200
100
20
2,000
Permethrin
10,000
200
100
20
2,000
Trifluralin
5,000
100
50
10
1,000
ECDC MIXTURE
Bcnlluralm
10,000
100
50
20
10
1,000
DDT-p,p"
10,000
100
50
20
10
1,000
Endosulfan Sulfate
10,000
100
50
20
10
1,000
Endrin
10,000
100
50
20
10
1,000
PCB 1221 + 1254 MIXTURE
Arochlor 1221
10,000
5,000
Arochlor 1254
10,000
5,000
PCB 1016+1260 MIXTURE
Arochlor 1016
10,000
100
5,000
rochlor 1260
10,000
100
5,000
SURROGATE MIXTURE
m
HRrachloro-m-Xylene
10,000
25
25
Dccachoro-Biphenyl
20,000
50
50
Clilordane Technical
10,000
1,000
600
300
100
5,000
To\aphenc Technical
10,000
5,000
2,000
1,000
600
o
o
C">
5,000
Arochlor 1016
10,000
1,000
600
300
100
Arochlor 1221
10,000
1,000
600
300
100
Arochlor 1232
10,000
1,000
600
o
o
r*->
100
5,000
Arochlor 1242
10.000
1,000
600
W
O
o
100
5,000
Arochlor 1248
10,000
1,000
600
o
o
CI
100
5,000
Arochlor 1254
10,000
1.000
600
O
o
m
100
Arochlor 1260
10,000
1,000
600
300
100
TABLE 5 PERCENT RECOVERY AFTER SULFURIC ACID CLEAN-UP
Parameter
%Recovery after
Sulfuric acid
Parameter
%Recovery after
Sulfuric acid
Aldrin
76
Benfluralin
-
Alpha-BHC
90
Alplia-Chlordane
not affected
Beta-BHC
80
Endrin
--
Delta-BHC
77
Clilordane
not affected
Gamma-BHC
82
PCB-1016
not affected
-------
Revision Date: 05/06/98
Author(s): Mei-Fang Shyu, K. Tate 1/\I\
VO-002-2
MEASUREMENT OF VOLATILE ORGANIC COMPOUNDS IN WATER BY
GAS CHROMATOGRAPHY/MASS SPECTROMETRY
1. SCOPE AND APPLICATION
1.1. This method details the analysis of purgeable organic compounds in water by purge & trap/ gas
chromatography/mass spectrometry. The following compounds may be determined by this
method:
acetone
1,1-dichloroethene
acetonitrile
cis-1,2-dichloroethene
benzene
trans-1,2-dichloroethene
bromodichloromethane
c/'j-l,3-dichloropropene
bromoform
trans-1,3-dichloropropene
bromomethane
1,4-dioxane
2-butanone (MEK)
ethylbenzene
carbon disulfide
2-hexanone
carbon tetrachloride
methylene chloride
chloroethane
4-methyl-2-pentanone (MIBK)
chlorobenzene
styrene
2-chloroethyl vinyl ether
tetrachloroethene
chloroform
1,1,2,2-tetrachloroethane
chloromethane
1,1,1-trichloroethane
or;/?o-chlorotoluene
1,1,2-trichloroethane
dibromochloromethane
trichloroethene
1,2-dichlorobenzene
trichlorofluoromethane
1,3-dichlorobenzene
toluene
1,4-dichlorobenzene
ort/io-xylene
dichlorodifluoromethane
;«eta-xylene//?ara-xylene
1,1-dichloroethane
vinyl chloride
1,2-dichloroethane
2. SUMMARY OF THE METHOD
2.1. The volatile compounds are introduced into the gas chromatograph by the purge and trap method.
The components are separated via gas chromatography and detected using a mass spectrometer,
which provides both qualitative and quantitative information. The described method is based on
EPA Method 624 Purgeables, Part 136, Title 40 and EPA Method 8260, SW-846. The procedures
described here are designed to meet or exceed both of these EPA methods. This is accomplished
by meeting the more stringent requirement from both methods. Please refer to the EPA methods
for additional details.
3. APPARATUS AND EQUIPMENT
3.1. Syringes: 5 (iL, 10 (.iL, 50 |iL, 5 mL, 10 mL, 50 mL
-------
3.3. 40 mL water sample vials
3.4. Teflon®/silicone septa
3.5. Gas Chromatographs: Hewlett Packard 5890 Series II gas chromatograph; Perkin-Elmer 8500 GC;
or Varian 3300 GC
3.6. Mass Spectrometers: Finnigan Magnum Ion Trap Detector; or 5971 Hewlett Packard Mass
Selective Device
3.7. Computers: IBM-compatible PC data collection system
3.8. Autosamplers: Dynatech PTA-30 W/S ; or Tekmar Precept II
3.9. Purge & Traps: Tekmar 3000; or OI Analytical 4460A
3.10. Tekmar or OI Analytical cryofocusing module
3.11. 230 Liter Liquid nitrogen dewer at 50 psi pressure
3.12. Sample Screening Detectors: OI Analytical 4430 PID/4420 ELCD
3.13. Sample Screening Autosamplers: Tekmar 2016 or OI analytical MPM-16 16-position autosampler
4. REAGENTS AND CHEMICALS
4.1. Solvents: Purge & Trap grade methanol, anhydrous ethylene glycol, and laboratory reagent water
(municipal water which has been filtered and distilled).
4.2. 25 ppm internal standards and surrogates solution:
4.2.1. Dispense accurately 5 mL each of Ultra Scientific STM-260 and STM-270 solutions into
a 200 mL volumetric flask containing 150 mL of 50/50 methanol and ethylene glycol.
Dilute this solution to volume with 50/50 methanol and ethylene glycol. The ethylene
glycol must be high quality and free of volatile compounds. The working standard is
stored at < 0.0°C and is prepared from new stock solutions every 3 months.
4.3. Working standards for QC checks and matrix spikes (second source):
The following standards are all purchased from AccuStandard in concentrations of 100 to 200
ppm in methanol: M-601-CHG, CLP-022, M-601C, M-8240C and M502-15. These standard
mixtures include all of the compounds analyzed in this method and are used as received. All stock
and working standards are stored at < 0.0 °C.
4.3.1. QC Checks:
4.3.1.1. A 2 ppb QC check is prepared from the mixture M-601-CHG every 12 hours.
Spike 4 uL of the 100 ppm M-601 -CHG standard into 200 mL of laboratory
water.
IM973.DOC
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4.3.1.2. A 10 ppb QC check is prepared from the mixture CLP-022 every 12 hours.
Spike 2.15 (iL of the 200 ppm CLP-022 standard into a 43 mL vial of laboratory
water.
4.3.2.3. QC checks for the other compounds are prepared only for those analytical tests
or samples which require the special compounds.
4.3.2. Matrix Spike Checks:
4.3.2.1. A 5 ppb matrix spike check is prepared from the mixture M-601-CHG every 10
samples. Normally, duplicate matrix spikes are prepared for every 20 samples.
Spike 2.15 nL of the 100 ppm M-601-CHG standard into a 43 mL sample vial.
4.4. Calibration Standards (primary source):
The following standards are all purchased in concentrations of 100 to 200 ppm in methanol from Ultra
Scientific: HC-070 (2-ch!oroethyl vinyl ether), HC-330 (or/Zio-chlorotoluene), HCM-601, BTX-100, CLP-
150 and PMX-141. These standard mixtures include all of the compounds analyzed in this method. All
stock and working standards are stored at < 0.0 °C. A list of the normal calibration levels is given below,
where a minimum of 5 levels are selected for calibration. Additional calibration levels may be prepared as
deemed necessary.
4.4.1. 0.20 ppb HCM + BTX + HC-070 + HC-330 calibration standard: prepare a 1:100
dilution of a solution containing 20 ppb HCM + BTX + HC-070 + HC-330.
4.4.2. 0.50 ppb HCM + BTX + HC-070 + HC-330 calibration standard: prepare a 1:10 dilution
of a solution containing 5.0 ppb HCM + BTX + HC-070 + HC-330.
4.4.3. 2.0 ppb HCM + BTX + HC-070 + HC-330 calibration standard: prepare a 1:10 dilution
of a solution containing 20 ppb HCM + BTX + HC-070 + HC-330.
4.4.4. 5.0 ppb HCM + BTX + HC-070 + HC-330 calibration standard: spike 4.3 |iL of 50 ppm
HCM + BTX (section 4.3.1), 2.15 jaL of HC-070, and 2.15 |iL of HC-330 into a 43 mL
vial of laboratory water.
4.4.5. 10 ppb HCM + BTX + HC-070 + HC-330 calibration standard: spike 8.6 nL of 50 ppm
HCM + BTX (section 4.3.1), 4.3 f.iL of HC-070, and 4.3 nL of HC-330 into a 43 mL vial
of laboratory water.
4.4.6. 20 ppb HCM + BTX + HC-070 + HC-330 calibration standard: spike 17.2 |iL of 50 ppm
HCM + BTX (section 4.3.1), 8.6 f.iL of HC-070, and 8.6 nL of HC-330 into a 43 mL vial
of laboratory water.
4.4.7. 0.20 ppb CLP-150 calibration standard: prepare a 1:100 dilution of a solution containing
20 ppb CLP-150.
4.4.8. 0.50 ppb CLP-150 calibration standard: prepare a 1:10 dilution of a solution containing 5
ppb CLP-150.
4.4.9. 2.0 ppb CLP-150 calibration standard: prepare a 1:10 dilution of a solution containing 20
ppb CLP-150.
4.4.10. 5.0 ppb CLP-150 calibration standard: spike 2.15 |iL of a solution containing 100 ppm
CLP-150 into a 43 mL vial of laboratory water.
IM973.DOC
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4.4.11. 10 ppb CLP-150 calibration standard: spike 4.3 \iL of 100 ppm CLP-150 into a 43 mL
vial of laboratory water.
4.4.12. 20 ppb CLP-150 calibration standard: spike 8.6 |iL of 100 ppm CLP-150 into a 43 mL
vial of laboratory water.
4.4.13. The PMX-141 calibration levels are prepared in the same fashion as the CLP-150
calibration standards, except the volumes from the stock standard are reduced by 50% to
adjust for the original stock concentrations.
4.5. Internal standards for sample screening: 20 ppm fluorobenzene (FB) and 50 ppm
bromochloromethane (BCM).
4.5.1. Dispense accurately 500 |iL of Ultra Scientific STS-170 (2000 ppm fluorobenzene in
methanol) and 1250 (iL of Ultra Scientific STS-180 (2000 ppm bromochloromethane in
methanol) into a 50 mL volumetric flask containing 25 mL of Purge & Trap grade
methanol. Dilute this solution to a final volume a 50 mL with methanol.
5. SAMPLE COLLECTION, PRESERVATION AND HANDLING
5.1. For each water sample a minimum of three 43 mL VOA vials are collected with Teflon®-lined
silicone septum caps. Samples are collected without headspace (no bubbles) and may be
preserved with 130 uL of a 6 M HCL solution. The samples are placed into a ziplock bag
(provided) which in turn is placed into a metal can.
5.2. Samples are stored in a locked, flammable-rated refrigerator at 4.0 ± 2 °C until time for analysis.
Waste samples are stored in a separate refrigerator from the water and soil samples.
5.3. Unpreserved samples must be analyzed within 7 days of collection.
5.4. Samples preserved with HC1 (pH <2) must be analyzed within 14 days of collection.
6. SAMPLE PREPARATION PROCEDURE
6.1. All glassware should be cleaned according to the glassware cleaning SOP VO-007.
6.2. The integrity of custody seals must be noted and recorded in the sample log.
6.3. The sample pH is tested with pH paper to determine the appropriate sample holding time. If the
pH is close to 2, then a more precise pH meter is used.
6.4. The sample vials are checked for headspace and upside down septa. Any problems are noted in
the sample log.
6.5. All samples other than blanks and duplicates should be bubble tested prior to analysis. The
bubble test is designed to identify samples which foam excessively during the purging process and
present a risk to the Purge &. Trap instrument.
IM973.DOC
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6.5.1. Place a 5 mL aliquot of sample into a sparge tube which is connected to 40 mL/min. air
flow and observe the amount of foam generated. If the foam from the sample approaches
the top of the sparger, then the sample must be diluted.
6.5.2. Record the dilution factor for later sample preparation.
6.6. Samples other than blanks and duplicates should be screened prior to GC/MS analysis. The
screening procedure is as follows:
6.6.1. Draw a 5 mL aliquot of sample into a 5 mL glass syringe. Then inject 5 |iL of the
internal standard screening solution into the end of the syringe.
6.6.2. Transfer the sample into a sparge tube, and finger tighten the sparge tube to the
instrument.
6.6.3. Based on the screening information, dilute the sample such that the analyte
concentrations will fall in the 5-50 ppb range.
6.5. Prepare samples by labeling the vials with the sample ID and performing any required sample
dilutions.
6.6. Select a sample for duplicate matrix spikes. The matrix spike sample should be selected randomly
from the samples in the batch, however some consideration should be given to the number of
available vials. Also, samples with headspace should not be used for the matrix spikes. The
matrix spike level is normally 5 ng/L, which is prepared by spiking 2.15 (iL of matrix spike
standard solution into each of the two sample vials. Mix well by gently rotating the vials on their
side.
6.7. Laboratory blanks should be prepared from the laboratory water supply and analyzed prior to
analysis of the samples.
7. SAMPLE ANALYSIS/QUANTITATION
7.1. Instrument Conditions - See SOP VO-008 for specific instrument set-up instructions.
7.2. The GC/MS system must be checked to ensure that acceptable performance criteria are achieved
for bromofluorobenzene (BFB) at the beginning of each day and every 12 hours thereafter for as
long as analysis are to be performed. This performance test must be passed and maintained
before any samples or standards are analyzed.
7.2.1. The internal standard and surrogate solution contains BFB as one of the surrogates.
Analysis of a 5-mL laboratory water blank, with 1 jiL of internal standard mix is injected
by the autosampler, and will serve as a GC/MS performance test.
7.2.2. Obtain the BFB mass spectrum and confirm that all of the m/z criteria in Table 1 are
achieved. If the criteria are not achieved, the operator must retune the mass spectrometer
and repeat the test until all criteria are achieved.
IM973.DOC
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Table l.-BFB m/z Abundance Criteria
Mass, m/z
Abundance Criteria
50
75
95
96
173
174
175
176
177
15-40 % of mass 95
30-60 % of mass 95
Base peak, 100 %
5-9 % of mass 95
<2 % of mass 174
>50 % of mass 95
5-9 % of mass 174
>95 % but < 101 % of mass 174
5-9 % of mass 176
7.3.
7.4.
7.5.
7.6.
A laboratory blank must be analyzed to demonstrate that interferences from the analytical
procedures are under control once the m/z abundance criteria has been achieved. The tuning
blank will suffice as a laboratory blank, provided that the tune check passes.
The analyst must demonstrate every 12 hours of operation that the calibration of the
instrumentation are under control through the analysis of QC check standards. This is
accomplished by analyzing a 2 ng/L check standard solution containing all of the compounds of
interest, other than the ketones which are spiked at a higher level. A 10 ug/L ketone check
standard solution is also prepared and analyzed. Only after achieving the QC acceptance criteria
can samples be analyzed. Some special request compounds may be added to the QC check
standard solution as needed.
Each blank, sample and spike is fortified with 1 j.iL of the 25 ppm internal standard/surrogate
solution by the autosampler.
Actual samples can be analyzed after achieving the QC acceptance criteria. The analysis sequence
should be similar to the following:
7.6.1. BFB tune check
7.6.2. Laboratory water blank
7.6.3. 2 ppb PQL check standard .every 24 hours
7.6.4. 5 ppb compound check standard every 12 hours
7.6.5. 10 ppb ketone check standard every 24 hours
7.6.6. Replicate laboratory fortified blanks
7.6.7. Laboratory water blank
7.6.8. Replicate matrix spikes
7.6.9. Laboratory water blank
7.6.10. Samples (including duplicate sample)
7.6.11. Laboratory water blank
IM973.DOC
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7.6.12. Laboratory fortified blank
7.6.13. Laboratory water blank
7.7. Check list before beginning GC run:
7.7.1. Check the GC temperature program.
7.7.2. Check the autosampler program.
7.7.3. Check the quantity of internal standard and liquid nitrogen.
7.7.4. Empty the autosampler waste bottle.
7.7.5. Fill the autosampler wash bottle with laboratory water and pressurize it.
7.7.6. Check the purge and trap parameter settings.
7.7.7. Setup the acquisition sequence in the instrument log and in the computer acquisition
program.
7.7.8. Check the acquisition parameters in the computer program.
7.7.9. Arrange the sample vials in the autosampler tray.
7.7.10. Double check the order of the sample vials to insure that it is consistent with the
computer acquisition and the instrument log.
7.7.11. All samples must have surrogate standards added to them in order to monitor the
performance of the laboratory equipment and practices. The Dynatech PTA-30 W/S
autosampler adds the internal standards and surrogates to the sample automatically.
7.7.12. The laboratory must analyze replicate matrix spikes for every ten samples analyzed
in order to assess possible complications resulting from sample matrix on the
accuracy and precision of the measurements.
7.8. The result of each analytical run should be examined promptly upon completion. Check to make
sure the internal standards and spikes are in the retention time window and the spectra are correct.
Also make sure the surrogates and spikes recoveries are acceptable.
7.9. For complete reporting procedures, refer to SOP VO-010 for specific reporting procedures.
8. DATA ARCHIVING
8.1. Finnigan ITD Magnum files:
8.1.1. Three different types of files are generated by the ITD instruments: a raw data file with
extension .MS (or .DAT; a quantitation file with extension .QD; and an ASCII file with
extension .MSQ.
IM973.DOC
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8.1.2. Raw data files generated from the ITD1 instrument should be transferred temporarily to
the network directory, TLHCHEM2WOCWOC1 (for files generated by the ITD2 and
ITD3 instruments use the subdirectories VOC2 and VOC3, respectively).
8.1.3. Transfer the files for the instrument VOC1 from the TLHCHEM2WOCWOC1 directory
to the archival directory TLHCHEM2\ARCHIVE\VOC\ VOC1 after the raw data are
reviewed and final reports are generated. The same is done with the data files generated
by the other ITD instruments, except the files are placed into their respective
subdirectories. The data is permanently archived on optical disk by the Computer
Support Group within the Bureau of Laboratories.
8.1.4. If the old raw data files need to be retrieved from the tapes, call the System Administrator
of the Computer Support Group and identify the instrument with which the data were
generated.
8.2. Hewlett Packard MSD files:
8.2.1. Files generated from the MSD instrument are composed of directories which contain the
raw data, quantitation results, and ASCII file.
8.2.2. For convenience, the data files may be transferred to the analyst's desk computer for
review after an analytical run is finished.
8.2.3. After the data files have been reviewed they must be moved to the network directory,
TLHCHEM2WOCWOCMSD for upload into the QC calculator.
8.2.4. The data files should be stored on the TLHCHEM2 drive for about two months after the
results have been reported in case the data needs additional review. The data should be
moved to TLHCHEM2\ARCHIVE\VOC\ VOCMSD for archival after the two month
holding period. The Computer Support Group will then archive the data permanently on
optical disks.
8.2.5 If old raw data files need to be retrieved from the tapes, call the System Administrator of
the Computer Support Group.
9. QUALITY CONTROL
9.1. The first sample of each day must be a laboratory water blank in order to demonstrate that
potential interferences from the analytical system are under control. Appropriate measures must
be taken to eliminate any interferences before sample analysis can begin.
9.2. The laboratory must demonstrate through the analysis of daily QC check standards that the
operation and calibration of the GC/MS system is in control. The calibration and QC acceptance
criteria are listed in the QA/QC plan for the Chemistry Section. If any parameter fails to meet the
acceptance criteria, appropriate troubleshooting/maintenance measures must be taken and a new
QC standard must be analyzed. The recovery results of the daily check standard are uploaded into
the QC database at the same time that the sample data are uploaded into the LIMS.
9.3. The laboratory must fortify all samples with surrogate standard solutions and calculate the percent
recovery of each surrogate compound. The surrogate recovery data is uploaded with the daily
check data into the QC database of the LIMS. The control limits are set at Avg. +/- 3Std, where
Avg. is the average recovery and Std is the standard deviation. Appropriate corrective measures
must be taken if the surrogate recovery values are outside of these limits and the affected
sample(s) must be reanalyzed.
IM973.DOC
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9.4. The laboratory must analyze duplicate matrix spiked samples for each sample analysis batch. The
accuracy (%Recovery) and precision (%RPD) are calculated for every pair of spikes and a
statistical analysis is performed on every 20 data points. The control limits are then set at R +/-
3s, where R is the average of %Recovery (for precision it is the average of %RPD) and s is the
standard deviation. Appropriate corrective measures must be taken if the analyte recoveries or
RPDs are outside of these limits and the affected samples must be reanalyzed. The spike
recoveries and statistical analysis are uploaded into the LIMS and printed in the final report for the
job.
9.5. For more specific information regarding QA/QC measures, see the SOP VO-OOl.
10. DETERMINATION OF METHOD DETECTION LIMITS
10.1. The MDLs were established using procedures given in EPA 40 CFR Part 40, Appendix B.
11. SAFETY/HAZARDOUS WASTE MANAGEMENT
11.1. See Safety SOP, OG-001.
12. REFERENCES
12.1. Code of Federal Regulations, Title 40, Part 136, Vol. 49, No. 209, Method 624: Base/Neutrals
and Acids. 10/26/84.
12.2. Test Methods for Evaluating Solid Wastes, Third Edition, SW-846, Method 8260. revision 2, 9/94.
IM973.DOC
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Revision Date: 05/06/98
Author: Mei-Fang Shyu,'K. Tate \£A5C'
VO-003-2
MEASUREMENT OF VOLATILE ORGANIC COMPOUNDS IN SEDIMENTS BY GAS
CHROMATOGRAPHY/MASS SPECTROMETRY
1. SCOPE AND APPLICATION
1.1. This method details the analysis of purgeable organic compounds in sediments by gas
chromatography/mass spectrometry. The following compounds may be determined by this
method:
acetone
1,1-dichloroethene
acetonitrile
cis-1,2-dichloroethene
benzene
trans-1,2-dichloroethene
bromodichloromethane
c/'.?-l,3-dichloropropene
bromoform
trans-1,3-dichloropropene
bromomethane
1,4-dioxane
2-butanone (MEK)
ethylbenzene
carbon disulfide
2-hexanone
carbon tetrachloride
methylene chloride
chloroethane
4-methyl-2-pentanone (MIBK)
chlorobenzene
styrene
2-chloroethyl vinyl ether
tetrachloroethene
chloroform
1,1,2,2-tetrachloroethane
chloromethane
1,1,1-trichloroethane
or//io-chlorotoluene
1,1,2-trichloroethane
dibromochloromethane
trichloroethene
1,2-dichlorobenzene
trichlorofluoromethane
1,3-dichlorobenzene
toluene
1,4-dichlorobenzene
ortho-xy\ene
dichlorodifluoromethane
weta-xylene/pwa-xylene
1,1-dichloroethane
vinyl chloride
1,2-dichloroethane
2. SUMMARY OF THE METHOD
2.1. The volatile compounds are introduced into the gas chromatograph by the purge and trap method.
The components are separated via gas chromatography and detected using a mass spectrometer,
which provides both qualitative and quantitative information. The described method is based on
EPA Method 8260, SW-846. The procedures described here are designed to meet or exceed both
of these EPA methods. This is accomplished by meeting the more stringent requirement from
both methods. Please refer to the EPA methods for additional details.
3. APPARATUS AND EQUIPMENT
3.1. Syringes: 5 jaL, 10 |iL, 50 |iL, 5 mL, 10 mL, 50 mL
3.2.
-------
3.3.
40 mL water sample vials
3.4. Teflon©/silicone septa
3.5. Gas Chromatographs: Hewlett Packard 5890 Series II gas chromatograph; Perkin-Elmer 8500 GC;
or Varian 3300 GC
3.6. Mass Spectrometers: Finnigan Magnum Ion Trap Detector; or 5971 Hewlett Packard Mass
Selective Device
3.7. Computers: IBM-compatible PC data collection system
3.8. Autosamplers: Dynatech PTA-30 W/S ; or Tekmar Precept II
3.9. Purge & Traps: Tekmar 3000; or OI Analytical 4460A
3.10. Tekmar or OI Analytical cryofocusing module
3.11. 230 Liter Liquid nitrogen dewer at 50 psi pressure
3.12. Sample Screening Detectors: OI Analytical 4430 PID/4420 ELCD
3.13. Sample Screening Autosamplers: Tekmar 2016 or OI analytical MPM-16 16-position autosampler
4. REAGENTS AND CHEMICALS
4.1. Solvents: Purge & Trap grade methanol, anhydrous ethylene glycol, and laboratory reagent water
(municipal water which has been filtered and distilled).
4.2. 25 ppm internal standards and surrogates solution:
4.2.1. Dispense accurately 5 mL each of Ultra Scientific STM-260 and STM-270
solutions into a 200 mL volumetric flask containing 150 mL of 50/50 methanol and
ethylene glycol. Dilute this solution to volume with 50/50 methanol and ethylene glycol.
The ethylene glycol must be high quality and free of volatile compounds. The working
standard is stored at < 0.0 °C and is prepared from new stock solutions every 3 months.
4.3. Working standards for QC checks and matrix spikes (secondary source):
4.3.1. The working standards for QC checks and matrix spikes are all purchased from
AccuStandard in concentrations of 100 to 200 ppm in methanol: M-601-CHG, CLP-022,
M-601C, M-8240C and M502-15. These standard mixtures include all of the compounds
analyzed in this method and are used as received. All stock and working standards are
stored at < 0.0 °C.
4.4. Calibration Standards (primary source)
The following standards are all purchased in concentrations of 100 to 200 ppm in methanol from Ultra
Scientific: HC-070 (2-chloroethyl vinyl ether), HC-330 (or//;o-chlorotoluene), HCM-601, BTX-100, CLP-
150 and PMX-141. These standard mixtures include all of the compounds analyzed in this method. All
stock and working standards are stored at < 0.0 °C. A list of the normal calibration levels is given below,
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where a minimum of 5 levels are selected for calibration. Additional calibration levels may be prepared as
deemed necessary.
4.4.1. Preparation of 100 ppb HCM + BTX + HC-070 + HC-330 working standard: spike 88 nL
of 50 ppm HCM + BTX, 44 nL of 100 ppm HC-070, and 44 |iL of 100 ppm HC-330 into
44 mL of laboratory water.
4.4.1.1. 10 ng HCM + BTX + HC-070 + HC-330 calibration standard: spike 100 |iL of
100 ppb working standard into 5 mL of laboratory water in a soil vial.
4.4.1.2. 20 ng HCM + BTX + HC-070 + HC-330 calibration standard: spike 200 nL of
100 ppb working standard into 5 mL of laboratory water in a soil vial.
4.4.1.3. 40 ng HCM + BTX + HC-070 + HC-330 calibration standard: spike 400 (iL of
100 ppb working standard into 5 mL of laboratory water in a soil vial.
4.4.1.4. 50 ng HCM + BTX + HC-070 + HC-330 calibration standard: spike 500 (iL of
100 ppb working standard into 5 mL of laboratory water in a soil vial.
4.4.1.5. 100 ng HCM + BTX + HC-070 + HC-330 calibration standard: spike 1000 ^L
of 100 ppb working standard into 5 mL of laboratory water in a soil vial.
4.4.2. Preparation of 100 ppb CLP-150 working standard: spike 44 nL of 100 ppm CLP-150
into 44 mL laboratory water.
4.4.2.1. 10 ng CLP-150 calibration standard: spike 100 |j.L of 100 ppb working standard
into 5 mL of laboratory water in a soil vial.
4.4.2.2. 20 ng CLP-150 calibration standard: spike 200 ^L of 100 ppb working standard
into 5 mL of laboratory water in a soil vial.
4.4.2.3. 40 ng CLP-150 calibration standard: spike 400 pL of 100 ppb working standard
into 5 mL of laboratory water in a soil vial.
4.4.2.4. 50 ng CLP-150 calibration standard: spike 500 |iL of 100 ppb working standard
into 5 mL of laboratory water in a soil vial.
4.4.2.5. 100 ng CLP-150 calibration standard: spike 1000 |iL of 100 ppb working
standard into 5 mL of laboratory water in a soil vial.
4.4.3. The PMX-141 calibration levels are prepared in the same fashion as the CLP-150
calibration standards, except the volumes from the stock standard are reduced by 50% to
adjust for the original stock concentrations.
4.5. Internal standards for screening: 20 ppm fluorobenzene (FB)/50 ppm bromochloromethane
(BCM).
4.6.1. Dispense accurately 500 pL of Ultra Scientific STS-170 (2000 ppm fluorobenzene in
methanol) and 1250 (iL of Ultra Scientific STS-180 (2000 ppm bromochloromethane in
methanol) into a 50 mL volumetric flask containing 25 mL of Purge & Trap grade
methanol. Dilute this solution to a final volume of 50 mL with HPLC grade methanol.
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5. SAMPLE COLLECTION, PRESERVATION, AND HANDLING
5.1. Sediment samples are collected and stored in glass jars with Teflon©-lined screw caps. The jars
are typically filled to the lid to minimize headspace.
5.2. Samples are stored in a locked, flammable-rated refrigerator at 4.0 ± 2 °C until time for analysis.
5.3. The holding time for sediment samples is no more than 14 days following collection.
6. SAMPLE PREPARATION PROCEDURE
6.1. All glassware should be cleaned according to the glassware cleaning SOP VO-007.
6.2. The integrity of custody seals must be noted and recorded in the sample log.
6.3. The sample jars should be inspected for loose lids or partially filled containers. Any sample
problems should be noted in the sample log.
6.4. A methanol extract of each soil sample is prepared for screening purposes. A 10 g portion of each
sample is extracted with 10 g of Purge & Trap grade methanol in a 44 mL vial. The sample and
methanol weights are recorded in the sample preparation log to three significant figures. Once the
methanol is added the extract must be thoroughly mixed using a Vortex mixer for up to 2 minutes.
Recoveries of the volatile compounds can be severely reduced if the sample is mixed too long or
vigorously.
6.5. The percent dry weight of sediment samples is determined by first weighing out 5-10 g of wet
sample into a weighing dish and drying the sample at 105 °C overnight. The percent dry weight is
equal to the (dry sample weight divided by the wet sample weight) times 100. Samples which may
pose a fire hazard should not be placed in the oven.
6.6. The methanol extracts must be allowed to settle or be centrifuged to prevent solids from entering
the sampling syringe. The extracts are screened at a dilution of 1000 on the GC/PID/ELCD
instrument.
6.6.1. Inject 5 ^L of the sample extract and 5 |iL of the FB + BCM internal standard into a
syringe containing 5 mL of laboratory water.
6.6.2. Transfer the sample into a sparge tube and finger tighten the sparge tube onto the 16-
position autosampler.
6.6.3. Based on the screening results, dilute the sample such that the analyte concentrations will
occur in the 5-50 ppb range.
6.6.3.1 If the screening results indicate that the sample contains high-level pollutants
(i.e. target analyte levels above the instrument detection limits are observed)
then the high-level method should be applied. In the high-level method the
sample extracts are diluted as needed into laboratory water and analyzed by
GC/MS. Please refer to water sample SOP, VO-002.
6.6.3.2. If the screening results from 6.4.3 indicate the sample contains low-level
pollutants (i e., target analyte levels above the instrument detection limits are not
observed) then the low-level method should be applied.
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6.7. The low-level method is based on the purging of a heated sediment sample mixed with laboratory
water. Approximately 5 g sample is weighed out and placed into a soil vial along with a magnetic
stir bar. A record of the sample weight is made in the sample preparation notebook. The
Dynatech PTA-30 W/S autosampler is equipped to automatically add laboratory water and the
surrogate and internal standards.
6.9. Laboratory water is placed in an empty soil vial and is analyzed as a laboratory blank.
6.10. A laboratory sand preparation is carried through the entire sample and weighing process, and is
analyzed as a laboratory sand blank. The laboratory sand is prepared by rinsing clean, white sand
with HPLC grade methanol and laboratory water several times. The rinsed sand is baked in a
muffle furnace at 200 °C overnight to remove any volatiles and is then stored in the VOC
laboratory oven. The heated laboratory sand is occasionally purged with carrier grade helium or
nitrogen to remove trapped volatiles.
6.11. Choose one sample for duplicate analysis and one sample for duplicate matrix spikes for every 10
samples analyzed.
6.11.1. 40 ng matrix spike: Spike 400 uL of a 100 ppb standard of M-601-CHG into the pair of
matrix spike samples.
6.12. Prepared samples may be stored overnight in the refrigerator, although it is preferable that
samples be prepared and analyzed on the same day,.
7. SAMPLE ANALYSIS AND QUANTITATION
7.1. Instrument Conditions - See SOP VO-008 for specific instructions on setting up VOC
instrumentation.
7.2. The GC/MS system must be checked to see if acceptable performance criteria are achieved for
BFB at the beginning of each day that analyses are to be performed and every 12 hours therafter
for as long as analysis are to be performed. This performance test must be passed before any
samples, blanks, or standards are analyzed.
7.2.1. The internal standard and surrogate solution contains BFB as one of the surrogates.
Analysis of a 5-mL laboratory water blank, with 1 ^L internal standards injected by the
autosampler, will serve as a GC/MS performance test. A tune check may be performed
on any sample since BFB is included as one of the surrogates.
7.2.2. Obtain a BFB mass spectrum and confirm that all of the m/z criteria in Table 1 are
achieved. If the criteria are not achieved, the analyst must retune the mass spectrometer
or repeat the test until all criteria are achieved. Usually, repeating the test will achieve the
criteria.
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Table 1 ,-BFB m/z Abundance Criteria
Mass, m/z
Abundance Criteria
50
15-40 % of mass 95
75
30-60 % of mass 95
95
Base peak, 100%
96
5-9 % of mass 95
173
<2 % of mass 174
174
>50 % of mass 95
175
5-9 % of mass 174
176
>95 % but < 101 % of mass 174
177
5-9 % of mass 176
7.3. A laboratory blank and sand blank must be analyzed to demonstrate that interferences from the
analytical system are under control. The tune blank will suffice as a laboratory blank, provided
that the tune check passes.
7.4. The analyst must demonstrate every 12 hours of operation that the calibration of the
instrumentation are under control through the analysis of QC check standards. This is
accomplished by analyzing a soil vial containing 40 ng of each target analyte as supplied in the
QC check standards. Some special request compounds may be added to the QC check standard
solution as needed.
7.5. Each sample, blank and spike is fortified with 1 |iL of the 25 ppm internal standard/surrogate
solution.
7.6. The methanol extracts are analyzed by GC/MS if the sample requires high-level analysis. This
procedure is the same as the analysis of water samples. Please refer to the water sample SOP VO-
002.
7.7. Actual samples can be analyzed after achieving the QC acceptance criteria. The analysis sequence
should be similar to the following:
7.7.1. BFB tune check
7.7.2. Laboratory water blank (soil mode)
7.7.3. 20 ng PQL compound check standard every 24 hours
7.7.4. 30 ng compound standard (optional)
7.7.5. 40 ng compound check standard every 12 hours
7.7.6. 40 ng ketone check standard every 12 hours
7.7.6. Duplicate 40 ng lab fortified blanks in sand
7.7.7. Laboratory water blank (soil mode)
7.7.8. Laboratory sand blank
7.7.9. Duplicate matrix spikes
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7.7.10. Laboratory water blank (soil mode)
7.7.11. Samples (including duplicate sample)
7.7.12. 40 ng lab fortified blank in sand
7.7.13. 40 ng ketone check standard in sand
7.7.14. Laboratory water blank (soil mode)
7.8. Check list before beginning GC run:
7.8.1. Check the GC temperature program.
7.8.2. Check the autosampler program.
7.8.3. Check the quantity of internal standard and liquid nitrogen.
7.8.4. Empty the autosampler waste bottle.
7.8.5. Fill the autosampler wash bottle with laboratory water and pressurize it.
7.8.6. Check the purge and trap parameter settings.
7.8.7. Set up the acquisition sequence in the instrument log and the computer acquisition
program.
7.8.8., Check the acquisition parameters in the computer program.
7.8.9. Arrange the sample vials in the autosampler tray.
7.8.10. Double check the order of the sample vials to insure that it is consistent with the
computer autosequence and the instrument log.
7.8.11. All samples must have surrogate standards added to them in order to monitor the
performance of the laboratory equipment and practices. The Dynatech PTA-30 W/S
autosampler adds the internal standards and surrogates to the sample automatically.
7.8.12. The laboratory must analyze replicate matrix spikes for every ten samples analyzed in
order to assess possible complications resulting from the sample matrix on the accuracy
and precision of the measurements.
7.9. The result of each analytical run should be examined promptly upon completion. Check to make
sure the internal standards and spikes are in the retention time window and the spectra are correct.
Also make sure the surrogates and spikes recoveries are acceptable.
7.10. For complete reporting procedures, refer to SOP VO-010.
8. DATA ARCHIVING
8.1. Finnigan ITD Magnum files:
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8.1.1. Three different types of files are generated by the ITD instruments: a raw data file with
extension .MS (or .DAT; a quantitation file with extension .QD; and an ASCII file with
extension .MSQ.
8.1.2. Raw data files generated from the ITD1 instrument should be transferred temporarily to
the network directory, TLHCHEM2WOCWOC1 (for files generated by the ITD2 and
ITD3 instruments use the subdirectories VOC2 and VOC3, respectively).
8.1.3. Transfer the files for the instrument VOC1 from the TLHCHEM2WOCWOC1 directory
to the archival directory TLHCHEM2\ARCHIVE\VOC\ VOC1 after the raw data are
reviewed and final reports are generated. The same is done with the data files generated
by the other ITD instruments, except the files are placed into their respective
subdirectories. The data is permanently archived on optical disk by the Computer
Support Group within the Bureau of Laboratories.
8.1.4. If the old raw data files need to be retrieved from the tapes, call the System Administrator
of the Computer Support Group and identify the instrument with which the data were
generated.
8.2. Hewlett Packard MSD files:
8.2.1. Files generated from the MSD instrument are composed of directories which contain the
raw data, quantitation results, and ASCII file.
8.2.2. For convenience, the data files may be transferred to the analyst's desk computer for
review after an analytical run is finished.
8.2.3. After the data files have been reviewed they must be moved to the network directory,
TLHCHEM2WOCWOCMSD for upload into the QC calculator.
8.2.4. The data files should be stored on the TLHCHEM2 drive for about two months after the
results have been reported in case the data needs additional review. The data should be
moved to TLHCHEM2VARCHIVE\VOC\ VOCMSD for archival after the two month
holding period. The Computer Support Group will then archive the data permanently on
optical disks.
8.2.5 If old raw data files need to be retrieved from the tapes, call the System Administrator of
the Computer Support Group.
9. QUALITY CONTROL
9.1. The first sample of each day must be a laboratory water blank in order to demonstrate that
potential interferences from the analytical system are under control. Appropriate measures must
be taken to eliminate any interferences before sample analysis can begin.
9.2. The laboratory must demonstrate through the analysis of daily QC check standards that the
operation and calibration of the GC/MS system is in control. The calibration and QC acceptance
criteria are listed in the QA/QC plan for the Chemistry Section. If any parameter fails to meet the
acceptance criteria, appropriate troubleshooting/maintenance measures must be taken and a new
QC standard must be analyzed. The recovery results of the daily check standard are uploaded into
the QC database at the same time that the sample data are uploaded into the LIMS.
9.3. The laboratory must fortify all samples with surrogate standard solutions and calculate the percent
recovery of each surrogate compound. The surrogate recovery data is uploaded with the daily
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check data into the QC database of the LIMS. The control limits are set at Avg. +/- 3Std, where
Avg. is the average recovery and Std is the standard deviation. Appropriate corrective measures
must be taken if the surrogate recovery values are outside of these limits and the affected
sample(s) must be reanalyzed.
9.4. The laboratory must analyze duplicate matrix spiked samples for each sample analysis batch
(batch not to exceed 20 samples). The accuracy (%Recovery) and precision (%RPD) are
calculated for every pair of spikes and a statistical analysis is performed on every 20 data points.
The control limits are then set at R +/- 3s, where R is the average of %Recovery (for precision it is
the average of %RPD) and s is the standard deviation. Appropriate corrective measures must be
taken if the analyte recoveries or RPDs are outside of these limits and the affected samples must
be reanalyzed. The spike recoveries and statistical analysis are uploaded into the LIMS and
printed in the final report for the job.
9.5. For more specific information regarding QA/QC measures, see the SOP VO-OOl.
10. DETERMINATION OF METHOD DETECTION LIMITS
10.1. The MDLs were established using procedures given in EPA 40 CFR Part 40, Appendix B.
11. SAFETY/HAZARDOUS WASTE MANAGEMENT
10.1. See SOP on Safety and Waste Managment, OG-OO1.
12. REFERENCES
12.1. Test Methods for Evaluating Solid Wastes, Third Edition, SW-846, Method 8260. revision 2,9/94.
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