Document 3evqa6VRrz1kxmg4JjqgQ90bD
Analysis #0615.01 Revision 01
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M,.-- 0,. 9,,
AR226-2725
2,,0,.,0,,1
FG-143 in WaterWastewater by SPME/GCMS
Reference:
1. Low-Level Determination of FC-143 in Wafer, CH2M Hil!^In^^^K^IQQI.
2. Method 8260B, Revision 2, SW-846, USEPA, DeGe^^^^JiFB Tuning)
Sarrion, M.N.; Santos, F.J.- Galceran, M.T.
3. In Situ Derivatization/Solid-Phase Mfcroexf/"a%6a. for ffi'i'Determination of
Haloacetic Acids in Water. Analytical
72, No. 201, October
15,2000, pp. 4865-4873.
4. SPME Applications Guide Builei
5. Agilent Technologies Op
Cross Reference: The following proceduras^^^refeTOnced in this document:
MC-EX-001, "GC/Hi;^^^fSR?e and Corrective Maintenance."
Scope: ^^Siis^^lSta--
This rnelais a|||Scableto the measurement of the ammonium perfluorooctanoate in
Thelimitofquantitationisl.Ou.g^L
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v Lancaster Laboratories
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Analysis #0615.01
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^. g.g^
Basic Principle:
Ethyl esters of the target and surrogate are converted from their respect^aci'. compounds using techniques for esterification. The sample is acidifie HCL. Ion paring agent, diethyl sulfate, ethanol and sulfuric acid are u acid into the ethyl esters. The sample is mixed on a stir plate at-
-"Sa;
specific time. The sample is then absorbed onto a 100 pm and injected into a GC/MS system equipped with a capill performed using internal standard calibration by GC/Mjg
Apparatus:
1. Hewlett-Packard Model 5890 (Se||
equivalent
6890 Gas Chromatograph or
2. Hewlett-Packard Model 59^^^^^y'5973 Mass Selective Detector or
3. Hewlett-Packard system or equ
pbftware, Thru-Put Systems Target data
4. Solid Pha
ction (SPME) - Supeico - 100 p.m
"".'UiSiSlHi
Polyd^l. ^fe^^^Be_ (PDMS) fiber, fiber pen for manual injection, and
injec^^Ql^y equivalent
Clear vial with Teflon/silicon septum or equivalent
Tate - VWR - mini stirrer, Model 200 or equivalent
;tir Bars -VWR Teflon stir bars Vz" X 5/16" or equivalent -
8. Disposable Glass pipettes
9. 10 mL Class A graduated cylinder
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.Lancaster Laboratories
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^AD"D ^n "a "MSM
10. Syringes-1 mL, 10 mL, 10 ^L, 25 }iL, 50 (U.
11. Timers - Capable of measuring time to 30 minutes, 12. Class A volumetric flasks, assorted sizes
13. Analytical balance-Capable of weighing to 0.000M1
.Ik A.
Reagents:
1. 1:1 HCL reagent grade or equivalent
2. Ethanol - AAPER Chemical - .s^Siii..--!Sas^r I's'-i.'"'
or equivalent
J^^aMB^OM 3.
Chromatography column .^"E'iisSH'^SSaiSi^- "''^^S'^''
x 0.25 mm ID, 1.0 pm df or
4. UPC helium for
5. Pentadecaflu^^^oic acid Ammonium salt -- Fluka, 98% pure or
- 2000 ppm BFB Chem Service ampulated solution in
Bitf^^ttlpi'ide or equivalent, for tuning agent and internal standard
afluorononanoic acid - Fluka, 97 % pure or equivalent for surrogate
itrabutylammonium hydrogen sulfate (TBA-HS) equivalent. Ion pairing reagent
Fluka, 99% pure or
9. Diethyl Sulfate -Aldrich, 98% or equivalent Ethylation reagent
10. Sulfuric Acid -ACS grade or equivalent
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^Lancaster Laboratories
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AsPppR BQ ^
2^00, 1
11. Deionized water
Standards:
Note: Working stocks are prepared by diluting stock solutions to j|he
concentration with a syringe and volumetric flask.
1. Stock Pentadecafluorooctanoic acid Arnmoniujca^l^EC-l?^- Weigh approximately 0.02 g pentadecafluorooctanisi^l'cid^^^einsaiultminto a 10 mL volumetric flask and dilute to volu^^^ethanoi. Record in database
or Dept 26 spikes and special mixes
is a stock solution.
2. Working Stock FC-143 -pentad Dilute the stock pentadecaflud
500 ppm using ethanol in
5Sn-..;;!"R;i.
lodalSoic
acid
ammonium
salt -
"!"
id ammonium salt solution to
3. internal standardf? 2000 ppm ampuj.H standard spik;
, volume, -sf
FB - 4-Bromofluorobenzene - Dilute
ition to 50 ppm in MeOH. This is the internal
~s'
tandards
and
samples
with
20
p-L
per
1
mL
of final
rononanoic acid surrogate - Weigh approximately 0.02 g
ip
nonanoic
acid
into
a
10-mL volumetric flask and
dilute to
y
hanol.
Record in database or Dept 26 spikes and special
>k. This is a stock solution.
sp
:ihg
Stock
Heptadecafluorononanoic
acid
-
Dilute the stock
ptadecafluorononanoic acid solution to 500 ppm using ethanol.
B--
6.
Ion Paring Agent -
Tetrabutylammonium hydrogen sulfate (TBA-HS) weigh
approximately (0.016 g to 100 mL deionized water)
7. Diethyl Sulfate solution 0.15 Molar in ethanol - 2mL of diethyi sulfate in 100 mL of ethanol.
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^IM Laboratories -
pncaster
^r 242 5 New Holland Pike Lancaster, PA 17601
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^PR 0 9
2801
8, Calibration Levels
Level 1: F1432.5: Level 2: F1435.0
25 pi. of calibration and surrogate intermediate + 10 pL of internal
standard
50 pi. of calibration and surroga|
intermediate + 10 pL of ^SSf^S^ '"Sal stanciard
i^Sa&Water,
?'1 HCL, -?
.0 mLs onized water, 1.5 mL 1:1 HCL,
Levels: F14310.0: Level 4: F14315.00:
100 p.L of calibration an^ffi^^
intermediate + 10 ^Ij^^yemar^y
standard
150 p.L of caiibr^^^^lftogate
intermedial^y^l'^B1'1^1""^
to 5.0 mLs deionized water, 0.5 mL 1:1 HCL, to 5.0 mLs deionized water,
standard^^^y^^^
0.5 mL 1:1 HCL,
Level 5: F14320.00: 200
and surrogate
to 5.0 mLs
i.pi. of internal
deionized water,
0.5 mL 1:1 HCL,
lit,.
BI9
Level 6: F14325.0,-'^^i(T^^calibration and surrogate
to 5.0 mLs
.sfe'^tfeediats + 10 p.L of internal
deionized water,
.i^^^^'starfdard
MDL/LOC^^^^^^. 10 pL of calibration and surrogate
0.5 mL 1:1 HCL, to 5.0 mLs
intermediate + 10 p.L of internal standard
deionized water 0.5 mL 1:1 HCL,
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^Lancaster Laboratories
2425 New Holland Pike Lanoster, PA 17601
Analysis #0615.01
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A, PR 0 9
2Q9t
Safety Precautions:
FC-143 is extremely dangerous in the neat room form. The time we|
exposure limits is 0.1 mg/m3. Therefore, extreme care must be working with this compound. Also, heating of the neat standajrd
concentrated solution must be avoided. Any handling oft .!
be done in a hood with a second analyst observing the
safety spotter.
luct must acting as a
The compounds used as surrogate standards are form hydrofluoric acid upon heating or breakdow
material to any concentrated solution mustbe||
4
Sample Preservation and Holding Tinre(
.erous!' These compounds Irthe exposure of the neat
Samples must be prepared within at time of ethylation.
late'collected. Extracts should be analyzed
Extracts and standards
20 to -10C prior to analysis.
Personnel Trainin^h^l^ftylications:
instrumental analysis will work with an experienced analyst
iey can independently calibrate the instrument, use the latifsystem to set up sequences, perform the calculations, interpret
PS, and enter the data into the LIMS. They will also follow the
mg manual for analysts. Proficiency is measured through ion audits of the tasks listed and overchecking of data.
Extraction/Ethylation Procedure:
NOTE: Prepare Standards/ Samples only when ready for analysis as variations in ethylation time-and absorption time will affect results. A timer is used which can measure two separate times, one for ethylation and one for absorption onto the fiber.
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i^ Laboratories Lancaster
F 2425 New Holland Pikt - Lancaster, PA 17601
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^g ^
1. Measure 5.0 mL of deionized water (standards) or sample into 15 mL clear vial and add 0.5 mL of 1:1 HCL to pH the solution below 3.
2. Spike Standards with appropriate amount of target and sun stock solution and samples with 50 pL of 500 ppm Heptade
..s-,.
acid surrogate solution. Add 10 p.L of 50 ppm BFB int vial prior to ethylation.
3.
Add a rinsed stir bar and 250 [iL of TBA-HSjas "<
Ate.. '"
4. Add 1.0 mL of 0.15 molar Diethyl
%!:?;;=,aI.;;;;:::!aalliia^5ii.r^Is:;^;;;:'
proof ethanoL
5. Cautiously add 10 drops, of conc|
"''SlagssasH5"
6. Recap vial tightly and placg.,,,^. ^^^^mini stirrer, Model 200, stir plate at speed 4 for 30.0 minute^^el^^ oelow),
7. Following the 30,OidTH^fc;igH|Miopnrocess, insert the 100 }^m PDMS fiber in its withdrawtn^s^tsjT^^settinogf 1.0 on the fiber pen through the
' Teflon/silicon^^l^' lower the fiber into the headspace for 10.0 minutes to
allow
Sfl^-the 8. raise the fiber into the up position and remove it from the pen .height from 1.0 to 3.6 on the fiber pen- Insert the pen je'ction port and lower the fiber into the port. Press the START
i
initiate the injection.
w
'
JQTE: Consistent speed rate and timing for the ethylation, absorption and nsertion steps greatly increases the reproducibility and precision of the method. Conditions above may change to increase sensitivity, reproducibility
and overall chromatography.
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-ancaster Laboratories
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API? n Q
" 3
WtwMl
GC/IV1S Analysis:
Instrument Setup
Detector Detector temperature Oven Temperature Program
Carrier -- Injection -
Mass selective detector (MSD)^
300C
45C for 3 minutes 70C/minute to fine for 10 minutes Helium, Cons;
Fiber in
Injector TemperatureInjection Mode -
The conditions listed abov&jrj overall chromatographyj^Bagff
sfsto split vent 40 mL/minute at 2 minutes i to improve the linearity, sensitivity, or S system.
nalyzing standards at 6 concentration levels and producing
S^.sv'
_,^The
relative
standard
deviation
of
the
response
factor
ie'iuitability of the average relative response factor for calculation of
;,..--
n
aliquot
of
0.5
ng/p.L
BFB
must
analyzed
and
meet the
criteria
described
in
_
Table 1. If the criteria are not met, the mass spectrometer must be retuned and BFB reanalyzed until all criteria are met. For BFB fiber analysis, Spike
50 pL of 50 ppm BFB working standard into 5.0 mL deionlzed water with
0.5 mL 1:1 HCLand place on the stir plate, insert the fiber pen, set to 1.0 through the septum and lower the fiber for 10.0 minutes. Raise the fiber, remove the pen and insert into the injection port. Start the injection.
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^Lancaster Laboratories
2425 New Holland Pike Lancaster, PA 17601
Analysis,#0615.01 Revision 01
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2001
2. If the performance criteria are met for the BFB solution, perform an.jnitial calibration by injecting the six calibration standard solutions refers
previously.
3. At the end of the calibration standard injections, inject the M1
The system must be able to detect FC-143 in the MDl^^si^pn. If the
system does not detect FC-143, then the tuning ar^^ir^^^^rocedure must be repeated under conditions that will yield^^tectionftr FC-143 in
the MDL/LOQ solution. Instrument maintena,pa^Bhed in MC-EX-001,
may be required.
4. Due to the nature of the techniqu
may require multiple
days for analysis. In the event
ries into a second day, prior to
resuming calibration standard i;
rijectand pass BFB as stated
previously, then inject a
ard from the already injected
standards and confirm Response factors mus'
ty response factor comparison.
% drift in order to continue with
calibration. lfthe%l
'20%, then corrective action and a new
te'De performed.
fctor for FC-143 and the PFNA surrogate for each
response factor (RF):
"A(x) = Area of the quantitation ion for the compound being measured C(is) = Concentration of the specific internal standard A(is) = Area of the quantitation ion for the specific internal standard C(x) = Concentration of the compound being measured
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I^LancasteLr aboratories
BF 2425 New Holland Rke Lancaster. PA 17601
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Q 9 App
"
WM
C. For FC-143 and the surrogate PFNA, calculate the mean RF from the Rj^ofthe ^
six calibration standards. Calculate the relative standard deviation:
%RSD =
SD x 1013 Avg RF
Where:
SD =
YRF-avgRF
='-------------
and
Avg
n-1
^"a
If the RSD of the response factors is
to 15%, then the
average relative response factor
If the %RSD
exceeds 15% then a linear curves^yA!,g''i^ftli-for quantitation.
D. Continuing calibrations
Verify the MS tune and initja'
shift during which analy;
it the beginning of every 12-hourwork
1. An aliquot oj
described^
be retys
.1^1
must be analyzed and meet the criteria If the criteria are not met, the mass spectrometer must Iteria are met. See A 1. above for injection procedure.
inBhuingcalibration check by injecting an aliquot of the mid-point
andard. Calculate the percent drift:
c^-c^ x 100 C(i)
Where: C(i) = Calibration check compound standard concentration C(c}' = Measured concentration using selected quantitation method
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-Lancaster Laboratories
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Analysis #0615.01
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Page 11 of 16
Q3 ^
The percent drift for FC-143 should not be greater than 120%. If the %drift
exceeds 20%, then corrective action must be taken and a new init"""55' calibration may need to be performed.
3. The absolute areas of the quantitation ions of the internal within -50% to +100% of the average area from the lastjniti
'Wa:.
the area for the internal standard is not within this win '-
action must betaken and documented.
4. The MDL/LOQ standard must be injected compliant continuing calibration check stand
^6&s..
FC-143 in the MDL/LOQ solution. Ifth
the tuning and calibration procedure
.a
will yield a detection for FC-143 i
& BFB and a ist be able to detect not detect FC-143, then d under conditions that solution. Instrument
maintenance as outlined in MC
e required.
Analysis of Samples:
1. Analyze a 5.0 mL aliquot <sSa -------- ""^. for the initial and contigjl
16extract under the same conditions used
;johs.
2. At the conclusiog
aguisition, use the same software to tentatively identify
peaks within tiajgji
___
LoftBme window of interest.
Examine the ion abundances of
.lii'.hiir.ii'^ii'.ia
component
SBatogram. If the ion abundance of the FC-143 ion used for
^anasi1'''
quantitatj,
ioNiXceeds the calibration range, dilute the aliquot and
il"_
^preparing dilutions, add sufficient internal standard to maintain
intration as that of the 1CAL.
COMPANY CONFIDENTIAL
Analysis #0615.01 Revision 01 Supersedes Date: None
EPfafgeceti1v2e oDfa1te6: A.iprnRRse wTM^
Qualitative Analysis:
^
A compound is identified by comparison of the sample mass spectrum (
background subtraction) with the mass spectrum of a standard of the ||J
(standard reference spectra). In order to verify identification, the fojlowfi)|
should be met:
'1(1
1. The sample component retention time should bej|iB|l@--10seSonds of the time
^iSS^Siiin^iS^iK-
observed for the component when a calibration^lu'l^^as analyzed.
2. All ions in the reference spectra at >10(%^^^^^^.abunda^tion should be
present in the sample mass spectra
within absolute 20%.
An example spectrum for the ethyl^9'ite>,r^^^fc:C-143 is presented in vss' sSw . ''"esr
Figure 1.
Quantitative Analysis:
Once a compound has been idi^^^ll^ytitation will be based on the internal standard technique and the^egr^^0Undance from the extracted ion current profile
(EICP) of the primary
Concentration
^^^"''^^^^^q"51"11^10" ion for the compound to be measured
Am||j,nt of internal standard added to the water sample (in micrograms)
A(is^flrf^!i of the quantitation ion for the appropriate internal standard
RF = Average response factor from the current initial calibration V(o) = Original water sample volume (in liters)
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I^LancasterLaboratories
y 2425 Hew Holland Pike Lancaster. PA 1760)
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",pr!pJ
Qu gs
^
""'
Quality Assurance:
At least one deionized water blank, laboratory control spike, and spike analyzed with every group. A matrix spike and matrix spike duplicate, analytical batch, unless insufficient client sample volume is supplied. LCSD must be substituted for the MS/MSD extraction. The spito analytes of interest. A surrogate standard spiking solution
dyg.ycafl
acid is also added.
The advisory QC windows are 70 - 130 for the mean
.-di
.
MS/MSD, and surrogate. If the recovery falls outs
may be taken based on the nature of the non be documented and may include reinjection
preparation of new calibration standards. acted upon once sufficient data points^
LCS/LCSD, lows, corrective action i corrective action must -w .instrument maintenance, and 'windows will be generated and
cted.
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J^Lancaster Laboratories
fir 24Z5 New Holland Pik.e Lancaster, PA 17601
Analysis #0615.01
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AP_ R Q 8
?0fif
a
a..
COMPANY CONFIDENTIAL
' ^Lancaster Laboratories
tgr 2425 New Holland Pike Lancaaei. PA 17601
Analysis #0615.01 Revision 01
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Effective Date: Page 15 of 16
^ gg
'
"
'
:
^M
COMPANY CONFIDENTIAL
I^LancasterLaboratories
Ef 2425 New Holland Pike . Lancaster, PA 17601
Analysis #0615.01
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Effective Date: w^ Page 16 of 16
. a *
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