8/31/18

NA

UNC

SOP No. KNOX-OP-0024, Rev. 0
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1.0 SCOPE AND APPLICATION
1.1

This SOP describes the procedure to be used for the extraction of HFPO-DA (CAS #13252-13-6) from Method 0010 Sampling Train matrices, including filters &associated rinses (“front-half”), XAD®-2 resin tubes & associated rinses (“backhalf”), impinger condensate composites (water), and from surface wipe samples.

1.2

This procedure does not describe the LC/MS/MS instrumental analysis of theextracts. For those details, see DV-LC-0012 “Analysis of Perfluorooctanoic Acid
(PFOA) and other Perfluorinated Hydrocarbons (PFCs) and PerfluorinatedHydrocarbon Sulfonates (PFSs) in Water and Soil by LC/MS/MS”.

1.3

Reporting limits will vary depending on sample volumes and dilution factors. See
Table 1 for reporting limits that are based on an assigned standard extract volume ofeach Method 0010 or Surface Wipe matrix.

2.0 SUMMARY OF METHOD
2.1

Front-Half Composites (particulate filter, probe, nozzle, and filter housing solvent
rinses) are extracted with methanol / 5% ammonium hydroxide (CH3OH / 5%
NH4OH) on a shaker table for 18 hours (minimum), filtered, and brought to a 1:1
volume with DI water / 5% ammonium hydroxide, then HFPO-DA is reformulatedwith 2% formic acid. A portion of the final extract is filtered through a polyethylene
disk filter for analysis.

2.2

Back-Half Composites (XAD®-2 resin tubes and back-half glassware solvent rinses)
are extracted with methanol / 5% ammonium hydroxide (CH3OH / 5% NH4OH) on a
shaker table for 18 hours (minimum), the extraction solvent is decanted and thesample is extracted a second time with fresh solvent for another 18 hours (minimum).
The extracts are combined and brought to a 1:1 volume with DI water / 5%ammonium hydroxide, then HFPO-DA is reformulated with 2% formic acid. A
portion of the final extract is filtered through a polyethylene disk filter for analysis.

2.3

Wipe samples are extracted with methanol / 5% ammonium hydroxide (CH3OH / 5%
NH4OH) on a shaker table for 18 hours (minimum), filtered, and brought to a 1:1
volume with DI water / 5% ammonium hydroxide, then HFPO-DA is reformulatedwith 2% formic acid. A portion of the final extract is filtered through a polyethylene
disk filter for analysis.

2.4

The volume of the Impinger Condensate Composite (water) samples are measured
and 1/20th of the sample is brought to 250 mL in DI water to send to Denver for
analysis.

2.5

13

C3 HFPO-DA is used in this analysis as an isotope dilution internal standard(IDA). The isotope dilution technique corrects the final analytical results foranalytical recovery losses encountered when analyzing more chemically complex
environmental samples. A known quantity of the labeled PFC compounds (IDA) is
added to every sample and to the batch quality control samples prior to extraction.
Because the isotopically labeled compound is chemically equivalent to the target
compound being evaluated, it is affected by interfering substances or target
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compound recovery losses from the samples to the same extent as the target
compound. The recovery of the labeled PFC’s is then used to mathematicallycorrect the final concentration results for the PFC’s.
3.0 DEFINITIONS
Refer to the Laboratory’s Quality Assurance Manual (QAM) for the Glossary of Terms,
Definitions and Acronyms except as follows:
3.1

HFPO-DA: 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-propanoic acid
(CAS # 13252-13-6)

3.2

IDA: Isotope-dilution internal analyte or standard

3.3

XAD®-2 resin: A porous polymeric adsorbent resin typically used for semivolatilecompound air sampling.

4.0 INTERFERENCES
4.1

Care should be taken not to cross-contaminate samples during the
preparation/extraction stages. An extreme range of concentrations are likely to be
encountered during sample handling, and appropriate sample handling, Isolation,and storage planning should be undertaken.

4.2

Approved solvents are demonstrated to be free from interferences by analysis oflaboratory method blanks.

5.0 SAFETY
5.1

Employees must abide by the policies and procedures in the Corporate
Environmental Health and Safety Manual (CW-E-M-001), Radiation Safety
Manual and this document.

5.2

This procedure may involve hazardous material, operations and equipment. ThisSOP does not purport to address all of the safety problems associated with its use.
It is the responsibility of the user of the method to follow appropriate safety, waste
disposal and health practices under the assumption that all samples and reagents arepotentially hazardous. Safety glasses, gloves, lab coats and closed-toe,nonabsorbent shoes are a minimum.

5.3

All work must be stopped in the event of a known or potential compromise to thehealth and safety of an associate. The situation must be reported immediately to alaboratory supervisor.

5.4

Specific Safety Concerns or Requirements
5.4.1

Eye protection that satisfies ANSI Z87.1 (as per the Environmental Health and
Safety Manual), laboratory coat, and nitrile gloves must be worn whilehandling samples, standards, solvents, and reagents. Disposable gloves thathave been contaminated will be removed and discarded; other gloves will becleaned immediately.

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5.4.2

5.5

Methanol is flammable and used throughout this procedure. Methanol should
be stored away from any ignition sources and kept in closed containers withsecondary containment measures or within a fume hood.

Primary Materials Used
The following is a list of the materials used in this method, which have a serious orsignificant hazard rating. Note: This list does not include all materials used in
the method. The table contains a summary of the primary hazards listed in
the SDS for each of the materials listed in the table. A complete list of materials
used in the method can be found in the reagents and materials section. Employees
must review the information in the SDS for each material before using it for the
first time or when there are major changes to the SDS.

Material(1)

Hazards

MethanolFlammable(MeOH)

PoisonExposure
Limit (2)Signs and symptoms of exposure

200 ppm(TWA)

A slight irritant to the mucous membranes. Toxic
effects exerted upon nervous system, particularly the
optic nerve. Symptoms of overexposure may include
headache, drowsiness and dizziness. Methyl alcohol
is a defatting agent and may cause skin to become
dry and cracked. Skin absorption can occur;
symptoms may parallel inhalation exposure. Irritantto the eyes.
Causes severe burns and possible irreversible eyedamage. May cause severe and permanent damage
to the digestive tract.

Irritant

Ammonium

Corrosive

25 ppmhydroxide

Toxic

(TWA)

Formic acidCombustibl
e

5 ppm
(TWA)

Causes severe burns, toxic by inhalation, harmful if
swallowed, possible sensitizer.

Corrosive
Flammable
Toxic
1 - Always add acid to water to prevent violent reactions.
2 - Exposure limit refers to the OSHA regulatory exposure limit.
5.6

Waste Management and Pollution Prevention
All waste will be disposed of in accordance with Federal, State and Local
regulations. Where reasonably feasible, technological changes have been
implemented to minimize the potential for pollution of the environment.
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Employees will abide by this method and the policies in section 13 of the Corporate
Safety Manual (CW-E-M-001) for “Waste Management and Pollution Prevention.”
6.0 EQUIPMENT AND SUPPLIES
6.1

6.2

Equipment
6.1.1

Shaker table apparatus for sample extractions

6.1.2

Volumetric Flasks (Class A): 100 mL

6.1.3

Graduated cylinder: 100 mL, 1000 mL

6.1.4

Hamilton glass syringe, 1 mL

Supplies
6.2.1

Glass disposable pipettes: 10 mL, 5 mL, 2 mL

6.2.2

Nalgene® containers: 1000 mL, 500 mL, 250 mL, 125 mL

6.2.3

Glass Fiber Particulate Filter: Glass fiber filters, without organic binder,
exhibiting at least 99.95% efficiency (< 0.05% penetration) on 0.3 μm
dioctyl phthalate smoke particles. Whatman 934-AH glass fiber filters are
the TestAmerica stock item used.

6.2.4

XAD®-2 Sorbent resin - Amberlite® XAD®-2 resin or equivalent (Supelco
Supelpak 2-SVM)

6.2.5

Disposable plastic syringe, 10-mL

6.2.6

Syringe filter, 0.45 µm

6.2.7

Disposable plastic funnel

6.2.8

Metal funnel

7.0 REAGENTS AND STANDARDS
7.1

Reagents
7.1.1

Reagent water is produced by a Millipore DI system or equivalent. Reagent
water must be free of the analyte of interest as demonstrated through theanalysis of appropriate method blanks.

7.1.2

Methanol (MeOH,) HPLC grade or equivalent

7.1.3

Ammonium hydroxide (NH4OH), ACS grade or equivalent

7.1.4

Formic acid, Reagent grade or equivalent

7.1.5

Extraction solvent: MeOH / 5% NH4OH:
50 mL NH4OH is brought to 1000 mL with MeOH

7.1.6

Diluent: Reagent water / 5% NH4OH:
50 mL NH4OH is brought to 1000 mL with DI water

7.1.7

2% Formic acid solution:
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20 mL formic acid is brought to 1000 mL with DI water.
7.2

7.3

Stock Standard Materials
7.2.1

13

7.2.2

HFPO-DA - Wellington, Catalog # - HFPO-DA, 50 µg/mL in MeOH

7.2.3

The stock standard solutions are stored at ≤6°C. Stock standard solutions
should be brought to room temperature before using. Standards aremonitored for signs of degradation or evaporation. Standard solutions must
be replaced at least annually from the date of opening or earlier if thevendor indicates an earlier expiration date

C3 HFPO-DA - Wellington, Catalog # - M3HFPO-DA, 50 µg/mL in
MeOH

Spiking Solutions (LCS & IDA)
7.3.1

All spiking solutions are stored in Nalgene® containers at ≤6°C and areassigned an expiration date of one year or earlier if the parent stock
materials have an earlier expiration date. Dilutions from stocks may not be
assigned expiration dates that exceed the expiration of the stock materials.

7.3.2

The LCS & IDA spiking solutions are prepared by diluting the appropriate
amounts of stock solutions in HPLC-grade methanol to a concentration of
0.5 µg/mL. The LCS spiking solution is also used to spike the MS and
MSD samples.

8.0 SAMPLE COLLECTION, PRESERVATION, SHIPMENT AND STORAGE
Sampling containers, preservation techniques and sample holding times are dependent on thespecific sample matrix, analytical method of choice, regulatory compliance requirements,
and/or specific contract or client requirements. Listed below are the assigned sample holding
times and preservation requirements.

SampleMatrixContainer

Preservation

Extraction
Holding Time

Impinger
Condensate(Waters)

Nalgene®

Cool ≤ 6oC

14 Days

Particulate
Filters

Nalgene®

Cool ≤ 6oC

14 Days

XAD®-2

Sampling
cartridge

Cool ≤ 6oC

14 Days

Surface Wipes

Nalgene®

Cool ≤ 6oC

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9.0 QUALITY CONTROL
9.1

9.2

The minimum quality controls (QC), acceptance criteria, and corrective actions aredescribed in this section.
9.1.1

Project-specific requirements can override the general requirements
presented in this section when there is a written agreement between theanalytical laboratory and the client (or client’s agent), and the source of
those requirements should be described in the project documents. Projectspecific requirements are communicated to the analyst via Method or
Sample Comments in TALS and the Quality Assurance Summaries (QAS)
in the public folders

9.1.2

Any QC result that fails to meet control criteria must be documented in a
Nonconformance Memo (NCM). The NCM is automatically sent to thelaboratory Project Manager by e-mail so that the client can be notified as
appropriate. The QA group periodically reviews NCMs for potential trends.
The NCM process is described in more detail in SOP KNOX-QA-0008.
This is in addition to the corrective actions described in the following
sections

Initial Performance Studies
The laboratory must establish a method detection limit (MDL) for each matrix. In
addition, an initial demonstration of capability (IDOC) must be performed by eachanalyst for each matrix. On-going proficiency must be demonstrated by each analyst
on an annual basis. See Section 13 for more details on detection limit studies, initialdemonstrations of capability, and analyst training and qualification.

9.3

Batch Definition
Batches are defined at the sample preparation stage. The batch is a set of up to 20
samples of the same matrix, plus required QC samples, processed using the sameprocedures and reagents within the same time period. Batches should be kept together
through the whole analytical process as far as possible, but it is not mandatory toanalyze prepared extracts on the same instrument or in the same sequence.

9.4

Method Blank (MB)One method blank must be processed with each preparation batch of 10 fieldsamples. The method blank is processed and analyzed just as if it were a sample.

9.5

9.4.1

The method blank for batches of aqueous samples consists of 250 mL of
Reagent DI water.

9.4.2

The method blank for batches of media samples (XAD®-2 resin, particulate
filter, surface wipe gauze pads) consists of the same matrix as used forcollection.

Laboratory Control Sample (LCS)At least one LCS must be processed with each preparation batch. The LCS is carriedthrough the entire analytical procedure just as if it were a sample.
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9.6

9.5.1

For aqueous sample batches, the LCS consists of 250 mL of Reagent DI
water.

9.5.2

For media collection samples (XAD®-2 resin, particulate filters, surface
wipes), the LCS consists of the same matrix as used for sample collection.

Isotopically Labeled Internal Standard (IDA)
Every field sample and QC sample (i.e. method blank, LCS, MS, and MSD) is spiked
with the isotope dilution internal standard compounds.

9.7

Summary of batch requirements

QC Sample

Frequency

Control Limit

Method Blank (MB)1 per batch≤ RL(batch = 1 to 20 samples)2

Lab Control Sample (LCS)

1 per batch

50 – 150%; 35%
RPD

Matrix Spike (MS)1,3,5

1 per batch, if applicable

50 – 150%

MS Duplicate (MSD) 1,3,5

1 per batch, if applicable

50 – 150%; 35%
RPD

IDA

Applied to each analytical& QC sample

50-200%6

1

Limits only apply if the sample concentration is ≤4X spike level; if sample concentrationis >4X spike level, limits do not apply and the data is flagged.
2

An LCS Duplicate (LCSD) is performed only when requested by the client/project/contract.

3

The sample selection for MS/MSD is randomly selected, unless specifically requested by aclient.
4

Statistical control limits are updated annually.

5

An MS/MSD set of analyses cannot be performed on an XAD®-2 resin material orparticulate filter sample.
6

Only applies to dilutions of up to 50x.

10.0 SAMPLE PREPARATION PROCEDURE
10.1

Front-half Composites (particulate filter and probe, nozzle, filter housing solvent
rinses)10.1.1 Align all front-half particulate filters sample fractions with their appropriate
solvent rinses on a counter. Solvent rinses are composed of methanol / 5%ammonium hydroxide.
10.1.2 Measure the volumes of the solvent rinses received for each of the samples
in order to determine the appropriate amounts of IDA spiking materials to
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be added to the samples, in addition to the amounts of other reagents to be
used in the sample preparations. These measured volumes are also used todetermine the final volumes that the samples to be brought to uponcompletion of the prep. See Table 2 for the proportions of reagents that
relate to the glassware solvent rinses received from the field.
10.1.3 The nominal final volume for a front-half sample is 50 mL made up by thefollowing reagents:

1 mL of 0.5 µg/mL IDA



22 mL of methanol / 5% ammonium hydroxide (includes field solvent
rinse volume)

22 mL of reagent water / 5% ammonium hydroxide

5 mL of 2% formic acid10.1.4 The particulate filters are placed into an appropriate Nalgene container for
preparation.
10.1.5 The particulate filters are initially spiked with the appropriate amount of
IDA and the front-half solvent rinses are then added to the sample.
Additional extraction solvent (methanol / 5% ammonium hydroxide) is
added to the sample in order to bring the volume of methanol / ammoniumhydroxide in the prep container up to the appropriate volume (in 22 mL
increments). For example, if a solvent rinse volume is 30 mL as received,
then the final total amount of extraction solvent with the rinse is 44 mL.
Therefore, 2 mL of IDA and 14 mL of methanol / 5% ammonium hydroxide
extraction solvent should be added to the sample and rinse in this example.
10.1.6 A particulate filter method blank and a particulate filter LCS are required
for this Method 0010 sample fraction preparation. Note that an additional 1
mL portion of a 0.5 µg/mL HFPO-DA native spike is added to the LCS
prior to the addition of extraction solvent.
10.1.7 Samples are extracted on a shaker table for a minimum of 18 hours.
10.1.8 After extraction of the front-half composite samples is completed, theextraction solvent is filtered into a separate appropriately sized Nalgene
container by placing a filter paper in disposable plastic funnels and pouring
the sample extracts through the funnels and into the Nalgene containers.
10.1.9 Enough reagent water / 5% ammonium hydroxide is then added to thesample to bring it to a 1:1 ratio with the original extraction solvent (i.e. 22
mL methanol / 5% ammonium hydroxide: 22 mL reagent water / 5%ammonium hydroxide).
10.1.10 A 2% formic acid solution is then added to each sample to achieve a ratioof 5 mL 2% formic acid for each 22 mL of methanol / 5% ammoniumhydroxide extraction solvent. Each sample is then mixed thoroughly.

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10.1.11 Approximately 5-6 mL of each front-half sample extract is filtered througha 0.45 µm polyethylene disk using a disposable, plastic syringe. The
remainder of the sample extract portions is archived in an appropriate
refrigerator.
10.2

Back-half Composite (XAD®-2 resin and back-half glassware solvent rinses)
10.2.1 Align and organize all back-half (XAD®-2) sample fractions with theirattendant solvent rinses on a counter. Solvent rinses are composed ofmethanol / 5% ammonium hydroxide (CH3OH / 5% NH4OH).
10.2.2 Measure and record the individual volumes of the rinses for each of thesamples in order to determine the appropriate IDA spike volumes to add tothe samples, in addition to the volumes of the other reagents used to prepare
the final sample extracts. The measured volumes are also used to determine
the final extract volumes for these samples. See Table 2 for the proportionsof reagents that relate to the glassware solvent rinses received from thefield.
10.2.3 The nominal final volume for a typical back-half composite sample extract
is 400 mL, which includes the following reagent volumes:

8 mL of 0.5 µg/mL IDA



176 mL of methanol / 5% ammonium hydroxide (includes fieldsolvent rinse

176 mL of reagent water / 5% ammonium hydroxide40 mL of 2% formic acid10.2.4 The XAD®-2 traps are emptied into an appropriate Nalgene container for
preparation.
10.2.5 The XAD®-2 resin samples are spiked with the appropriate volume of IDA(typically 8.0 mL). The XAD®-2 samples undergo a dual extraction process;therefore approximately half of the back-half solvent rinse is added to the
XAD®-2 for the first extraction. The remaining rinse is saved for later
addition during the second extraction cycle. Additional extraction solvent(CH3OH / 5% NH4OH) is added to the extraction container to bring thevolume up to a total of 88 mL minimum (or more in 22 mL increments).
10.2.6 A XAD®-2 method blank and XAD®-2 Laboratory Control Sample (LCS)
are required to be included with this preparation batch. The LCS is spiked
with both IDA and native HFPO-DA. Therefore, an additional 8 mL of a
0.5 µg/mL HFPO-DA native spike is added to the LCS prior to the additionof extraction solvent.
10.2.7 Samples are extracted on a shaker table for a minimum of 18 hours.
10.2.8 After the first 18 hour extraction cycle is completed for the samples, theextraction solvent is decanted into an appropriate labeled Nalgene containerand set aside for combination with the later solvent extraction fluid.
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10.2.9 The remaining back-half solvent rinse sample received from the field is
added to the XAD®-2 sample from the shaker table followed by the additionof an appropriate volume of extraction solvent to bring it up to a total of 88
mL minimum (or more in 22 mL increments).
10.2.10 Repeat the second extraction with fresh solvent on a shaker table for aminimum of 18 hours.
10.2.11 After the second extraction cycle of back-half samples is completed, thesolvent from both extraction cycles are combined with the XAD®-2 media.
10.2.12 Reagent water / 5% ammonium hydroxide is then added to the sample tobring it to a 1:1 ratio with extraction solvent (e.g. 176 mL methanol / 5%ammonium hydroxide: 176 mL reagent water / 5% ammonium hydroxide).
10.2.13 A 2% formic acid solution is finally added to each sample to provide aratio of 5 mL 2% formic acid for each 22 mL of methanol / 5% ammoniumhydroxide extraction solvent. Each sample is then mixed thoroughly.
10.2.14 Approximately 5-6 mL of the final back-half composite sample extract isfiltered through a 0.45 µm polyethylene disk using a disposable, plastic
syringe. The remainder of the sample extract portions is archived in an
appropriate refrigerator.
10.3

Surface Wipe Samples
10.3.1 The nominal final volume for a Surface wipe sample extract is 50 mL,
which includes the following reagents:

1 mL of 0.5 ug/mL IDA



22 mL of methanol / 5% ammonium hydroxide

22 mL of reagent water / 5% ammonium hydroxide

5 mL of 2% formic acid10.3.2 Note: If 22 mL of extraction solvent (methanol / 5% ammoniumhydroxide) is not enough to cover the wipe and allow the liquid to freely
flow while shaking, an additional 22 mL of the extraction solvent, alongwith an additional 1 mL of IDA, is added to the container. Additional
increments of the extraction solvent may be added until sufficient coverageis achieved for the extraction process to proceed properly.
10.3.3 The surface wipe samples are individually placed into an appropriate
Nalgene container for preparation.
10.3.4 The surface wipe samples are spiked with the appropriate amount of IDA
and the extraction solvent (CH3OH / 5% NH4OH) is added to the extraction
container.
10.3.5 A surface wipe method blank and LCS are required for this preparation.
Note that an additional 1 mL portion of a 0.5 µg/mL HFPO-DA native spikeis added to the LCS prior to the addition of extraction solvent.
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10.3.6 Samples are extracted on a shaker table for a minimum of 18 hours.
10.3.7 After extraction of the surface wipe samples is completed, the extraction
solvent is transferred to a separate appropriate Nalgene container using aclean methanol-rinsed metal funnel (no filter paper is necessary)
10.3.8 Use a glass rod or the end of a disposable pipet to press the extracted
surface wipe gauze against the bottom of the funnel to press out as much
extraction solvent as reasonable from the surface wipe media.
10.3.9 Reagent water / 5% ammonium hydroxide solution is added to the sample
to bring it into a 1:1 ratio with extraction solvent (e.g. 22 mL methanol / 5%ammonium hydroxide requires 22 mL reagent water / 5% ammoniumhydroxide).
10.3.10 A 2% formic acid solution is added to each sample at a ratio of 5 mL 2%
formic acid: 22 mL of methanol / 5% ammonium hydroxide extraction
solvent. Each sample is then mixed thoroughly.
10.3.11 Approximately 5-6 mL of each surface wipe sample extract is filteredthrough a 0.45 µm polyethylene disk using a disposable, plastic syringe.
The remainder of the sample extract portions is archived in an appropriate
refrigerator.
10.4

Condensate samples
10.4.1 In order to calculate the total mass of HFPO-DA present in an individual
Condensate Sample, the volume of liquid condensate as received ismeasured and recorded. The data is entered into a TALS batch in the “Vol
Collected” column.
10.4.2 Routinely, the initial volume of Condensate sample processed in extraction
is 1/20th of the total condensate volume. After the total volume isdetermined, 1/20th of the condensate sample is diluted to 250 mL using D.I.
water. The volume of Condensate sample used is recorded in the TALS
batch in the “Vol Cond. Used” column. The remaining sample is archived
in refrigerated storage.
10.4.3 The diluted sample portion is shipped to the Denver Laboratory for
extraction using SOP DV-OP-0019, section 10.5.

10.5

Sample Analysis
Extracted samples are shipped to the Denver Laboratory for analysis of HFPO-DA
following SOP DV-LC-0012.

11.0 CORRECTIVE ACTION
When circumstances are encountered that are not specifically delineated in the analytical SOPor the corrective actions listed do not adequately address, a Non-Conformance Memo (NCM)
will be initiated and the analyst should use his/her best analytical judgment and available
resources to determine the best corrective action to be taken. The situation may be caused bymore than one variable. The analyst should report the incident and seek the assistance from
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his/her immediate supervisor, QA manager or other experienced staff. The analysis of projectsamples should not be resumed until the source of the problem and an in-control status is reestablished. All samples associated with this should be reanalyzed after in-control status has
been re-established or if authorization is received from the supervisor or QA Manager for
release with data qualification. See SOP KNOX-QA-0008 for guidance on NonConformance procedures.
12.0 CALCULATIONS / DATA REDUCTION
12.1

Concentration, µg/Sample = C x V x Df x Fraction of sample extracted *Where:
C = sample concentration in extract (µg/L)
V = Volume of extract (L)Df = Dilution Factor
12.1.1 Example calculations per fraction at the reporting limit (where the calibration
reporting limit is 0.5 µg/L)
Particulate Filter & Surface Wipe = 0.5 µg/L x 0.050 L = 0.025 µg/sample
XAD®-2 = 0.5 µg/L x 0.40 L = 0.200 µg/sample
Condensate* = 0.5 µg/L x 0.005 L = 0.0025 µg/sampleParticulate Filter & Surface Wipe prep = 1 sample / 50 mLXAD®-2 prep = 1 sample / 400 mLCondensate prep = 1 sample* / 5 mL*

Condensate Sample: adjustment is made for the total volume of sample asreceived, and the total volume used in the extraction (e.g. if 1 sample = 200 mL,
and 10 mL is extracted, then RL increases by 200/10 = 20x).
12.2

Documentation and Record Management
12.2.1 All sample preparation and analytical batch information, including the batch
number(s), a list of samples being prepped, preparation analyst and date,identifications and amounts of reagents and standards used, andidentification of all measuring equipment used (e.g., balances,
thermometers, pipettes) are recorded in TALS.
12.2.2 Raw data is scanned or saved directly as a PDF and is attached to theanalytical batch in TALS.
12.2.3 The initial batch review is performed by the analyst and a second-level
review is performed by the area supervisor or designee.

13.0 METHOD PERFORMANCE
13.1

Method Detection Limit Study (MDL)

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The method detection limit (MDL) is the lowest concentration that can be detected fora given analytical method and sample matrix with 99% confidence that the analyte ispresent. MDLs reflect a calculated (statistical) value determined under ideal
laboratory conditions in a clean matrix, and may not be achievable in allenvironmental matrices. An initial method detection limit study is performed inaccordance with SOP CA-Q-S-006. The laboratory maintains the MDL study records
for analyses performed; these are verified quarterly (or when samples are
extracted/analyzed).
13.2

Demonstration of Capabilities
All personnel are required to perform an initial demonstration of proficiency(IDOC) on the instrument they will be using for these analyses, prior to testingclient samples. On-going proficiency must be demonstrated annually. IDOCs andon-going proficiency demonstrations are conducted as follows.
13.2.1 Four aliquots of the QC check sample are analyzed using the same proceduresthat are used to analyze samples, including the sample preparation steps. The
concentration of QC check samples should be approximately equivalent to a
mid-level calibration point.
13.2.2 Calculate the average recovery percentage and standard deviation of therecovery percentage for each analyte of interest.
13.2.3 If any analyte does not meet the acceptance criteria, the test must be
repeated. Only those analytes that did not meet criteria in the first test need
to be reevaluated. TNI 2009 requires that the analyst achieve consecutive
passing results. Repeated failure for any analyte indicates the need for thelaboratory to carefully evaluate the analytical procedure and take corrective
action.
13.2.4 Until the IDOC is approved by the QA Manager (or designee); the trainer
and trainee must be identified in the batch record.
13.2.5 Further details concerning demonstrations of proficiency are described in
SOP KNOX-QA-0009.

13.3

Training Requirements
The Group Leader is responsible for ensuring that this proficiency demonstration
procedure is performed by an associate who has been properly trained in its use andhas the required experience. A new analyst must work under documented
supervision prior to approval of the IDOC. Documentation that a new analyst is
performing under on-going supervision must be entered into the batch record (View
Batch Information) until that analyst’s IDOC has been approved by the QAManager (or designee). See requirements for demonstration of analyst proficiency
in SOP KNOX-QA-0009.

14.0 POLLUTION CONTROL
It is TestAmerica’s policy to evaluate each method and look for opportunities to minimize
waste generated (i.e., examine recycling options, ordering chemicals based on quantity
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needed, preparation of reagents based on anticipated usage and reagent stability). See
KNOX-HS-0005, Waste Minimization Program. Employees must abide by the policies in
Section 13 of the Corporate Environmental Health and Safety Manual (CW-E-M-001) for“Waste Management and Pollution Prevention.”
15.0 WASTE MANAGEMENT
Waste management practices are conducted that are consistent with all applicable rules andregulations. Excess reagents, samples and method process wastes are disposed of in an
accepted manner. Waste description rules and land disposal restrictions are followed.
Waste disposal procedures are incorporated by reference to KNOX-HS-0002.
15.1

The following waste streams are produced when this method is carried out:
15.1.1 Methanol waste – Flammable Solvent waste stream
15.1.2 Acidic waste – Acid waste stream
15.1.3 Caustic waste – Caustic waste stream
15.1.4 Solid waste generated by this procedure such as disposable pipette tips andextraction bottles are collected and turned into the Waste Coordinator forincineration in the incineration waste stream containers.
15.1.5 Expired Chemicals/Reagents/Standards – Contact Waste Coordinator16.0 REFERENCES / CROSS-REFERENCES
16.1

DV-LC-0012 “Analysis of Perfluorooctanoic Acid (PFOA) and other
Perfluorinated Hydrocarbons (PFCs) and Perfluorinated Hydrocarbon Sulfonates(PFSs) in Water and Soil by LC/MS/MS”

16.2

DV-OP-0019 “Extraction of Perfluorooctanoic Acid (PFOA) and Perfluorooctanoic
Sulfonate (PFOS) and other Perfluorinated Hydrocarbons (PFCs) in Water and
Soil”

16.3

EPA Method 0010 “Modified Method 5 Sampling Train”

16.4

EPA Method 3542A “Extraction of Semivolatile Analytes Collected Using Method0010 (Modified Method 5 Sampling Train)”

16.5

KX-QAM “Quality Assurance Manual

16.6

KNOX-QA-0008 “Nonconformance and Corrective Action”

16.7

KNOX-QA-0009 “Personnel Orientation and Training”

16.8

KNOX-HS-0002 “Waste Handling Procedures”

16.9

KNOX-HS-0005 “Waste Minimization Program”

16.10 CA-Q-S-006 “Detection and Quantitation Limits”
16.11 CW-E-M-001 Corporate “Environmental Health and Safety Manual”
17.0 METHOD MODIFICATIONS / CLARIFICATIONS
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This procedure has been developed and optimized for the expressed purpose of deriving
best practices for the characterization of HFPO-DA from flue gases sampled with Method0010 sampling trains. Removal of HFPO-DA requires the use of methanol as an extraction
fluid, and matrix matching for the utilization of EPA Method 8321A (LC/MS/MS). Other
laboratory modifications may be necessary as required by changes to the sampling train
made by the field team. This SOP presents the best practices demonstrated during themethod development process, such as the most effective solvent system used to extract thevarious sampling train fractions, and need for a double extraction cycle of the XAD®-2
fraction to increase the extraction efficiency.
18.0 TABLES/ATTACHMENTS
Table 1: Standard Reporting Limits
Table 2: Reagent Ratio Guide
Attachment 1: Example bench extraction sheet
19.0 REVISION HISTORY
Revision 0, dated July 23, 2018

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Table 1: Standard Reporting Limits
Condensate(g/sample)

FilterXAD®-2Wipe(g/sample)(g/sample)(g/sample)

0.0025

0.025

0.200

0.025

C3-HFPO-DA(0.5 µg/mL)

H2O / 5%
NH4OH

Formic Acid

Final Extract

Volume Added

Volume Added

Prepared Volume

HFPO-DASee section 12.1 for nominal initial/final volume

Table 2: Method 0010 Reagent Ratio Guide
Probe & Nozzle
Rinse Volume as
Received From
the Field

IDA Spike
VolumeAdjusted Volume
13(CH3OH / 5%
NH4OH)(CH3OH / 5%
NH4OH)< 22 mL

22 mL

1 mL

22 mL

5 mL

50 mL

< 44 mL

44 mL

2 mL

44 mL

10 mL

100 mL< 66 mL

66 mL

3 mL

66 mL

15 mL

150 mL< 88 mL

88 mL

4 mL

88 mL

20 mL

200 mL< 110 mL

110 mL5 mL

110 mL25 mL

250 mL< 132 mL

132 mL6 mL

132 mL

30 mL

300 mL< 154 mL

154 mL

7 mL

154 mL35 mL

350 mL< 176 mL

176 mL8 mL

176 mL

40 mL

400 mL

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Attachment 1: Example extraction bench sheet

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Attachment 1: Example extraction bench sheet (continued)

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