v>EPA
United States
Environmental Protection Agency
^ Office of
jr Research and Development
National Human Exposure Assessment Survey
(NHEXAS)
Region
Quality Systems and Implementation Plan
for Human Exposure Assessment
Notice: The U.S. Environmental Protection Agency (EPA), through its Office of Research and Development (ORD), partially funded
and collaborated in the research described here. This protocol is part of the Quality Systems Implementation Plan (QSIP)
that was reviewed by the EPA and approved for use in this demonstration/scoping study. Mention of trade names or
commercial products does not constitute endorsement or recommendation by EPA for use.
Research Triangle Institute
Research Triangle Park, NC 27079
Cooperative Agreement CR 821902
Field Operations Protocol
EPA-Compendium
Title: Compendium of Methods for Analysis of Metals and
VOCs in Water
Source: U.S. Environmental Protection Agency
U.S. Environmental Protection Agency
Office of Research and Development
Human Exposure & Atmospheric Sciences Division
Human Exposure Research Branch
378herb00.pdf ~ R-EPA.pdf
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FIELD
OPERATIONS
PROTOCOL
RESEARCH TRIANGLE INSTITUTE
POST OFFICE BOX 12194
RESEARCH TRIANGLE PARK, NC 27709-2194
EPA-Compendium
Page 1 of 88
TITLE: COMPENDIUM OF METHODS FOR ANALYSIS OF METALS AND VOCs IN
WATER
SOURCE: U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Office of Research and Development
Cincinnati, OH 45268
AUTHOR(s):
U.S. Environmental Protection Agency
Date:
Date:
Date:
APPROVED BY:
Principal Investigator:
QA Officer:
1*1
Not Applicable
Date:
Date:
STATUS:
IN PROGRESS: ~
DRAFT: ~
FINAL VERSION: [X]
REVISIONS:
No. Date
No. Date
++
©
6
1
7
2
8
3
9
4
10
5
11
t Effective date of this version is the date of the last approval signature;
revision 0 is the original version.
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EPA-Compendium
Revision 0
Page 2 of
COMPENDIUM OF METHODS FOR ANALYSIS OF METALS AND VOCs IN WATER
TABLE OF CONTENTS
Method 200.8 ~
Method 524.2
Determination of Trace Elements in Waters and Wastes by
Inductively Coupled Plasma-Mass Spectrometry
Measurement of Purgeable Organic Compounds in Water by
Capillary Column Gas Chromatography/Mass Spectrometry
Arsenic Method — To be provided by EPA
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>
Mrmnn 524 2 MEASUREMENT OF PURGEABLE ORGANIC COMPOUNDS IN MATER BY
HETHOO 524.Z. COLUMt GAS CWWMTOOUUW/lttSS SPECTROHETRY
Revision 4.0
August 1992
A. A1ford-Stevens, J. M. Elchelberger, and M. L. Budde
Method 524, Revision 1.0 (1983)
R. M. Slater, Jr.
Revision 2.0 (1986)
j. M. Elchelberger, and M. L. Budde
Revision 3.0 (1989)
j. v. Elchelberger, J. N. Hunch, and T. A.Bellar
Revision 4.0 (1992)
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
5
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NETHOO 524.2
urtciwcvnrr of PUR6EABLE ORGANIC COMPOUNDS IN WATER BY
CAPILLARY COLUMN GAS CHROMATOGRAPHY/MASS SPECTROMETRY
1. ^Pf APPLICATION
11 This is , general
neous neasurwent of pu^eable voiauie * #f treatllent
water, ground ;*^r; ™jL?U»ble to a wide range of organic co«H
following compounds can be determined by this method.
Compound
Acetone*
Acrylonitrile*
Ally! chloride*
Benzene
Bromobenzene
Bromochloromethane
Bromodi chloromethane
Bromoform
Bromomethane
2-Butanone*
n-Butylbenzene
sec-Butyl benzene
tert-Butylbenzene
Carbon disulfide*
Carbon tetrachloride
Chloroaceton i tri1e*
Chlorobenzene
1-Chlorobutane*
Chloroethane
Chloroform
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
Oi bromochloromethane
1,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Dibromomethane
1.2-Dichlorobenzene
1.3-Di chlorobenzene
1.4-Dichlorobenzene
trans-1,4-Di chloro-2-butene*
Dichlorodi f1uoromethane
Chemical Abstract Service
p«.gUtrv Number
67-64-1
107-13-1
107-05-1
71-43-2
108-86-1
74-97-5
75-27-4
75-25-2
74-83-9
78-93-3
104-51-8
135-98-8
98-06-6
75-15-0
56-23-5
107-14-2
108-90-7
109-69-3
75-00-3
67-66-3
74-87-3
95-49-8
106-43-4
124-48-1
96-12-8
106-93-4
74-95-3
95-50-1
541-73-1
106-46-7
110-57-6
75-71-8
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1.1-01chloroethane J* 34 3
1.2-01chloroethane ?e"SS i
1.1-01 chl oroethene
c1s-l,2-01chloroethene |||-« «
trans-1,2-01 chloroethene 156-60-5
1.2-01chloropropane J
1.3-D1 chl oropropane
2,2-01chloropropane *u i
1,1-01 chl oropropene J
1,1-01 chl oropropanone*
cls-1,3-D1chloropropene 10061-01 5
trans-1,3-01chloropropene 10061-OZ 6
Diethyl ether* 100-41-4
Ethyl benzene 'jg J* *
Ethyl methacryl ate* \
Hexachlorobutad1ene |'-®J *
Hexachloroethane*
2-Hexanone* 591-/8-©
I sopropyl benzene
4-Isopropyltoluene « Jj' 2
Methacrylonltrlle* oS~Ii 3
Methyl aery late* 7SISI2
Methylene chloride 75 09 Z
Methyl iodide* Zl"5 6
Methylmethacrylate* ®0-62 6
4-Methyl -2-pentanone* gj-jJ 1
Methyl-t-butyl ether* 161? iSli
Naphthalene jji il ,
Nitrobenzene* " X
2-Nitropropane*
Pentachloroethane* '
Propionltrlle* 105 i!-i
n-Propylbenzene 100-42-5
1JU 1?2-T etrachl oroethane
1,1,2,2-Tetrachloroethane 79 34 5
Tetrachloroethene }« JJ
Tetrahydrofuran* *
Toluene 1
1.2.3-Tr i chlorobenzene JJ-JJ •
1.2.4-Tri chlorobenzene izo-g-j
1.1.1-Trichloroethane 71-55-6
1.1.2-Tri chloroethane 79-00 5
Trichloroethene JJ "i .
Tr1 chl orof 1 uoromethane
1.2.3-Trichloropropane JJ'iJ'J
1.2.4-TrImethylbenzene 95-63-6
1.3.5-Trimethylbenzene 108-67-8
Vinyl chloride «"«»;}
r^vle™ 1W-38-!
Xylene l"6"42"3
New Compound 1n Revision 4.0
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1 2 Method detection 11«tts (HOLs) (3) are co«pourvd. Instrument and
especially matrix dependent and vary from
ua/l The applicable concentration range of this LE y
column and matrix dependent, and Is approxlMt«1y 0.02 to M M1
l.. _ wirfa-hnrp thick-film capillary column 1s used, narrow core
^in-flTi coluiins My have a capacity which Units the range to about
0 02 to 20 M9/L. Volatile water soluble, polar compounds which Ihave
relatively foi purging efficiencies can be f termlned using t
method. Such compounds may be more susceptible to matrix effects,
and the quality of the data may be adversely influenced.
1 3 Analytes that are not separated chromatographic^ly, but which have
different mass spectra and nonlnterferlng quantitation Ions (Jjble
1), can be Identified and measured 1n the same calibration or
water sample as long as their concentrations are somewhat JiBl1aJ*
?Sect Analytes that have very similar mass ?P«*" "nnot
be individually Identified and measured in the same
¦ixture or water sample unless they have different retention times
(Sect 11.6.3). Coeluting compounds with very s1«11 ar mass *P«J;tra,
typically many structural isomers, must be reported as an
group or pair. Two of the three isomeric xylenes a"Jt*» ?£,~ Ly
three dichlorobenzenes are examples of structural lsomers that may
not be resolved on the capillary column, and if not, must be reporxea
as Isomeric oairs. The more water soluble compounds (> 2% solublll
ty) and compounds with boiling points above 200#C are
water matrix with lower efficiencies. These analytes may be more
susceptible to matrix effects.
2. OP METHOD
2 1 Volatile organic compounds and surrogates^]th low
are extracted (purged) from the sample matrix by bubbling an
gas through the aqueous sample. Purged sample components are trapped
in a tube containing suitable sorbent materials. When purging Is
J^lete the sorbent tube 1s heated and backflushed with helm, to
desorb the trapped sa*>le components into a ca|^Jl*rL|?s ^"column
raohy (6C) column interfaced to a mass spectrometer (MS). The column
is tLoerature programed to facilitate the separation of the method
analvtes which are then detected with the MS. Compounds eluting from
the GC column are identified by comparing
and retention times to reference spectra a"d Jl® aiiiSfesare
j.i. k... Reference spectra and retention times for anaiyxes are
rtUlSU iy the leasurMBnt of calibration standards under the s«
conditions used for samples. The concentration of each Identifleo
colwonent ls ieasured by relating the MS response of the quantitation
1on^produced by that compound to the MS response °f the }"a"^at1on
ion produced by a co*>ound that is used as an Internal standard.
Surroaate analytes, whose concentrations are known in every sample,
are measured with the same Internal standard calibration procedure.
3. DEFINITIONS
¦* i tntfrnal STANDARD (IS) — A pure analyte(s) added to a sample,
extract, orltandafd solutloS In known amount(s) and used to measure
8
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5 js»tc i'SSirr-tsie1 « sst-sa-
must be an analyte that Is not a sample component.
3.2 SURROGATE ANALYTE (SA) -- A pure an;l^e<^^s°addl/toTlUlple
unlikely to be found in extraction or other processing and
aliquot in known ^4?„Ud ?! *a?ure other sa«ple
The %£?o?\he SA 1s to »nitor «thod perfor~.ee
with each sample.
3.3 LABORATORY DUPLICATES (LD1 and UK) -- Two aliquot* of the sa*
s»ple taken l^^tD mEKit ? £?sU associated
wit^laboratoryprocedures^butnot with sa*l, collection, preser,.-
tlon, or storage procedures.
3.4 FIELD ®U^JCATES (F01 and F02) -- Two separate saaples collected^at
sample collection, preservation and storage,
tory procedures.
3.5 LABORATORY REAGENT BL^ (LRB) -- An alrecentwate^
2&TS ft*""'are! equip™,
Mrs asw-aa ass £; £»».«rs>™.
present in the laboratory environment, the reagents, or ine pp
tus.
3.6 FIELD REAGEHT BLANK (FRB, _ An algrt jf-qent^ater or^er
blank matrix that is plia resoects including shipment to the
SSSi JlfM Interferences are present In
the field environment.
3.7 LABORATORY JjKT-j
* • isr
precise measurements.
SS^W2«i."SS«- £
9
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EBp3Sw""SaS££srSS:
assrJa a s&rsws g.'srssA'^rsi-.
concentrations.
1 in crnr* ¦STANDARD SOLUTION (SSS) — A concentrated solution containing
31 I»T«thod inalytes prepared In the 1»bor«tory using assayed
referen« materials or purchased fro. a reputable co»erc1.1 source.
•" S&sasSSBS ilsS&SSr
analyte solutions.
used to calibrate the instrument response with respect to analy
concentration.
"S«H5s£!^HS5£Klfr
test materials.
4. HfTFWFERENCES
• ¦ Bsfs^es^s' smms;?:
SSSis a
and regenerate the molecular sieve purge gas filter. Subtracting
blank values fro* sample results Is not permitted.
blanks should be analyzed to check for cross-contamination.
4 3 Special precautions nust be taken to determine
The analytical and sample storage area should be Isolated fro. all
10
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4.4
atmospheric sources of 3n°^S2u
ground levels will J as lines and purge gas plumbing should
Teflon tubing, al l GC carrier ga ^ {u£(ngy Laboratory .
SriSSsSJaS^SSH
before standards are prepared In the methanol.
safety
5.1
2 wSS^SS'
potential health h»«rd, ™d ® Jesponsib1e for maintaining awareness
sST^aSa^tei-JKi-A'"
(4-6) for the information of the analyst.
i.2 The following benzene! carbon
chloride. Pure standard d i hood> A NIOSH/MESA approved
Z?c gawesplrator should be wornwhen the .n.lyst handles h1,h
concentrations of these toxic compounds.
FT1TPff*fT iMP SUPPL1ES
C 1 campi f CONTAINERS - 40-mL to 120-mL screw cap vials each equipped
6.1 SAMPLE COHiAiHtw „i„_ prior to use. wash vials and
with a Teflon faced silicone sept * . riutilled water Allow
w^smsS&ISSlSSSiieB
6.2
^ H S,« V3Tin anYre. known t. *
free of organics.
purge AND TRAP SYSTEM — The purge and trap system consists ofthree
of the following specifications.
6.2.1
Th« all alass Durging device (Figure 1) should be designed to
accept 25-mL samples with a water column at least 5 cm deep.
,"5;," /K \ nuraina device is recommended if the GC/M5
t. obtain the jetho.i detec-
~ limits reauired. Gaseous volumes above the sample must
bl kepi io a -?niSSi (< 15 .1) to «l1.)n«te dead volu-
11
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6.2.2
rr *e a flUss frit should be installed at the base of the
Sample chamber so thedgXi8lMP5S\tdSte?of*< T-i at
l^causlKrlnsir^n?^ prob-
lems.
Ssiaffli!las"ffiaS£^a.s
of coconut charcoal. If 1 . can wg eliminated and
dichlorodifluoromethane, the trap. Before ini-
5^ th« '"p/rr^iytouS^t;r?«np0'hoSi5bec^l"«d
HrSSSHSis^ls:,,.
in Sect. 9.
6.2.3
The use .f the «thy, silicone co.ted^pacj^ ^^ed,
at the trap inlet.
SffferSSSSfiSSw
design^Illustrated 1n Fig. I meets these criteria.
6.3 GAS CHROMATOGRAPHY/MASS SPECTROHETER/DATA SYSTEM (SC/MS/OS)
mss
lers so that the colum flw rite will remain constant
throughout desorptlon and ^"'"Xo^^T'a sibi-
{KrtlE controller SiiniW, be required. If syringe
6.3.1
12
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6.3.2
Injections of 4-brooofluorobenzene (BFB) will be used, a
split/splitless Injection port Is required.
C»P" 1
10 2 4 1) Separations of the calibration mix-
5 Ss"srSiri2s as r ^sffi i
oSllmd co^ounS re^ntion t1«es for these columns .re
listed 1n Table 2.
6 3 2 1 Column 1 -- 60 . x 0.75 * IO VOCOl (Supelco Inc )
glass wide-bore capillary with a 1.5 m f"» thlck-
ness.
fnlumn 2 — 30 ¦ X 0.53 mm ID DB-624 (J&W Sclen-
tlflc? Inc.) fused silica capillary with a 3 m film
thickness.
6.3.3
. • 4a y o 32 mi ID DB-5 (0&VI Scientific,
ftlTf'us'ei s1l"ca capillary with a\ m fll- thick-
ness.
rolumn 4 75 m x 0.53 mm Id DB-624 (0&W Scien-
Sflc!I Inc.) fused silica capillary with a 3 m filn
thickness.
interfaces between the GC and MS. The Interface used depends
on the coluim selected and the gas flow rate.
-3.3.. The^lde-bore t^
"quired An open split Interface (7) or an
all-alass jet separator 1s an acceptable Interface.
Anv Interface can be used If the performance sPe^~
flcatlons described in this method (Sect. 9andl0)
5 £1IrK?Sod The end of the transfer line after
interface or the end of the analytical column
1f no Interface 1s used, should be placed within a
few ran of the MS 1on source.
Vthen narrow bore column 3 1s used, a cr*y®9en^
interface olaced just 1n front of the column Inlet
5 smelted! This Interface condenses the desorbed
sample components In a narrow band on an uncoated
fused silica precolumn using liquid n^r°5er liL
ina When all analytes have been desorbed from the
tro the Interface 1s rapidly heated to transfer
them'to the analytical column. The end of the ana-
lytical column should be placed within a few mm o
the HS 1on source. A potential problem with
1 nterface 1 s blockage if the Interface by frozen
6.3.3.2
13
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6.3.4
water from the trap. This condition will result In
a major loss 1n sensitivity and chromatographic
resolution.
The mass spectrometer must be capable of electron Ionization
It a electron energy of 70 eV. The spectrometer must
be capable of scanning from 35 to 260 amu with a ««p1ete
scan cycle time (including scan overhead) of 2 sec or 'es*-
(Scan cycle time ¦ Total MS data acquisition time In seconds
divided by number of scans In the chromatogram.) The SP*V
trometer must produce a mass spectrum that meets all
in Table 3 when 25 ng or less of 4-bromofluorobenzene (BFB)
is Introduced Into the GC. An average spectrum across the
BFB GC peak may be used to test Instrument performance.
ft i k An interfaced data system 1s required to acquire, store,
reduce, and output mass spectral data. T|l® ^g^MS^Iu'bv
ehnnld have the capability of processing stored GC/M5 data oy
recognizing a 6C peak within any given retention «Mw,
eomoarlng the mass spectra from the GC peak wltn sPe«rai
data in a user-created data base, and generating *
tentatively Identified compounds with ^eir.r?^J?"t^Je!he
and scan numbers. The software must allow integration of the
ion abundance of any specific 1on between specified time or
scan nwber 11«i ts. The
tion of response factors as defined 1n Sect. 10-Z-o
construction of a linear or second order regression calibra-
tion curve) calculation of response factor statistics (mean
and standard deviation), and calculation of
analytes using either the calibration curve or the equation
in Sect. 12.
6.4 SYRINGE AND SYRINGE VALVES
6.4.1 Two 5-mL or 25-mL glass hypodermic syringes with Luer-Lok tip
(depending on sample volume used).
6.4.2 Three 2-way syringe valves with Luer ends.
6.4.3 Micro syringes - 10, 100 ill.
6.4.4 Syringes - 0.5, 1.0. and 5-mL, gas tight with shut-off valve.
6.5 MISCELLANEOUS
6 5.1 Standard solution storage containers — 15-mL bottles with
Teflon lined screw caps.
7. RfftOTT? STANDARDS
7.1 TRAP PACKING MATERIALS
7 11 2 6-Diphenylene oxide polymer, 60/80 mesh, chromatographic
grade (Tenax GC or equivalent).
14
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7.1.2 Methyl silicone packing (optional) — OV-1 (3%) on Chromosorb
W, 60/80 mesh, or equivalent.
7.1.3 Silica gel — 35/60 mesh, Davison, grade 15 or equivalent.
7 14 Coconut charcoal — Prepare from Barnebey Cheney, CA-580-26
lot #M-2649 by crushing through 26 mesh screen.
REAGENTS
7.2.1 Methanol — Demonstrated to be free of analytes.
7.2.2 Reagent water ~ Prepare reagent water by tap water
through a filter bed containing about 0.5 kg of activated
carbon, by using a water purification system, or by boll ng
distilled water for 15 mln followed by a Inert
qas while the water temperature 1s held at 90°C. Store In
clean, narrow-mouth bottles with Teflon lined septa and screw
caps.
7.2.3 Hydrochloric acid (1+1) ~ Carefully add measured volume of
conc. HC1 to equal volume of reagent water.
7 2.4 Vinyl chloride — Certified mixtures of vinyl chloride 1n
nitrogen and pure vinyl chloride are available from several
sources (for example, Matheson, Ideal Gas Products, and Scott
Gases).
7.2.5 Ascorbic acid — ACS reagent grade, granular.
7.2.6 Sodium thiosulfate — ACS reagent grade, granular.
STOCK STANDARD SOLUTIONS ~ These solutions may be purchased as
certified solutions or prepared from pure standard materials using
the following procedures. One of these solutions is required for
every analyte of concern, every surrogate, and the Internal standard.
A useful working concentration is about 1-5 mg/mL.
7 3 1 Place about 9.8 ml of methanol into a 10-mL ground-glass
stoppered volumetric flask. Allow the flask to stand,
unstoppered, for about 10 min or until all alcohol-wetted
surfaces have dried and wcljh to the nearest 0.1 ihq*
7 3 2 If the analyte is a liquid at room temperature, use a 100-jiL
syringe and immediately add two or more drops of reference
standard to the flask. Be sure that the reference standard
falls directly into the alcohol without contacting the neck
of the flask. If the analyte 1s a gas at room iemPer;t"re»
fill a 5-mL valved gas-tight syringe with the standard to the
5.0-mL mark, lower the needle to 5 mm above the methanol
meniscus, and slowly inject the standard into the neck area
of the flask. The gas will rapidly dissolve in the methanol.
15
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7 3 3 Rewelqh, dilute to volume, stopper, then mix by Inverting the
flask several times. Calculate the concentration in nq/nL
from the net gain 1n weight. When compound P*"*^is cert1-
fled at 96% or greater, the weight can be used w^hout cor-
rection to calculate the concentration of the stock standard.
7 3 4 Store stock standard solutions In 15-mL bottles equipped with
Teflon lined screw caps. Methanol solutions °*,
trlle, methyl Iodide, and methyl acrylate are stable for only
one week at 4*C. Methanol solutions prepared from other
liquid analytes are stable for at least * weeks when stored
at 4°C. Methanol solutions prepared from 9as^us a"a1j£?s t
are not stable for more than 1 week when stored at < 0 C,
room temperature, they must be discarded after 1 day.
primary DILUTION STANDARDS — Use stock standard solutions to prepare
wtoSy dilution standard solutions that contain all the analytes of
ZSEtfZR prepared X'SMSSi tlu "Mlly
calf brat 1 on sol ut1 ons. Storage Ums described for stock standard
solutions 1n Sect. 7.3.4 also apply to prlaary dilution standard
solutions.
FORTIFICATION SOLUTIONS FOR INTERNAL STANDARD AND SURROGATES
7 5 1 A solution containing the internal standard Malik?316
compounds 1s required to prepare 1aborat°rV *nd
falso used as a laboratory performance check solution),
{o fortif? Jach sample. Prepare a fjrttfieition solution
containing fluorobenzene (internal standard), 1,2- dlchloro
benzene-d, (surrogate), and BFB (surrogate) in methanol at
concentrations of 5 pg/mL of each (any appropriate -
tion Is acceptable). A 5-/»L aliquot of this *°]J**0"
to a 25-mL water sample volume gives concentrat 1
of each A 5-tfl aliquot of this solution added to a 5-mL
water sample volume gives a concentration of 5 (ig/L of each.
Additional Internal standards and surr°gate analytes are
optional. Additional surrogate compounds should be similar
1P„ physical and chemical characteristics to the analytes of
concern.
5 PREPARATION OF LABORATORY REAGENT BLANK (LRB) --Fill J 25-mL (or
?.«n svrinae with reagent water and adjust to the mark (no air
bubbles). Inject an appropriate volume of the fortIfication solution
containing the Internal standard and surrogates Jhr5JJ9h A"
valve Into the reagent water. Transfer the LRB to the purgl g
device. See Sect. 11.1.2.
16
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7.7 PREPARATION OF LABORATORY FORTIFIED BLANK --
like a calibration standard (Sect. 7.8). This is a can oration
standard that is treated as a sample.
7.8 PREPARATION OF CALIBRATION STANDARDS
7.8.1 The number of calibration solutions (CALs) needed depends on
the calibration range desired. A minimum °f £AL solu
tions is required to calibrate a range of a factor of 20 In
concentration. For a factor of 50, use at least four stan-
dards awl for a factor of 100 at least five standards. One
calibration standard should contain each ¦tioS°llSit
at a concentration of 2-10 times the Si. Itli-
(Tables 4, 5, and 7) for that compound. The other CAL stan
dardsshouldcontain each °L"^ernEe^r5°2ALnlo?a-
tions that define the range of the method. Every cal soiu
tion contains the internal standard and the surrogate com-
pounds at the same concentration (5 iiq/l suggested for a 5-mL
sample; 1 Mg/L a 25-mL sample).
7 8 2 To prepare a calibration standard, add an appropriate volume
of a primary dilution standard containing all analytes of
concern to an aliquot of acidified 5 i«j/l, adetemina-
tion of the amount of the chlorine may be necessary.
Diethyl-p-phenylenediamine (DPD) test kits are c°™ercially
available to determine residual chlorine in the Add
an additional 25 m of ascorbic acidper «"* 5 "?'1 t
residual chlorine. If compounds boiling below 25 C are not
to be determined, sodium thiosulfate may be used to reduce
the residual chlirine. Fill sample bottles to overflowing,
but take care not to flush out the rapidly dissolving ascor
bic acid. No air bubbles should pass through the Js
the bottle is filled, or be trapped in tne sample when the
bottle is sealed. Adjust the pH of the duplicate samples to
17
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8.1.2
8.1.3
8.1.4
< 2 by carefully adding two drops of 1:1 HC1 for
ar:ws % rai? saarA
sodium thlosulfate with the HC1 prior to sampling.
When sampling from a water tap, open the tap
rsrs, a. f» w»
i!!d »11«t 5Uplic»t.'S»pl.$ fro. the fl<*.1n9 strM.
5r3SHrSi'?^^^:
«tirrina Check the pH with narrow range (1.4 to 2.8) pH
paper. Recordthe nuiber of drops of acid necessary to
nU to 2 To collect actual samples, refill tne
large container with fresh swple ^P°ursa»ple1nt^M*U
vials Follow filling Instructions 1n Sect. 8.1.1. am 1
fate according to Sect. 8.1.1.
to ensure that they will arrive at the Juratory wltn
substantial amount of Ice remaining 1n the cooler.
tf a camole foams vigorously when HC1 1s added, discard that
analyzed within 24 hr of collection time.
2 SAMPLE STORAGE
8.2.1
8.2.2
e. _ i t ^ j«r until analysis. The sample storage
area must be free of organic solvent vapors and direct or
intense light.
Analyze all samples within 14 days of collection. Samples
not analyzed within this period «ist be discarded and re-
placed.
.3 FIELD REAGENT BLANKS (FRB)
r i i Duollcate FRBs must be handled along with each sample set,
8,3 SUlch's coiSposed of the samples collected fro. the s«e
18
-------
noneral sanle site it approximately the same tilt. At the
"•« blink sample bottles wlth r«gent
water and sample preservatives, seal, and ship to the:sam-
pling site along with empty sample bottles and back to the
laboratory with filled sample bottles. Wherever a set of
samples Is shipped and stored, It is accompanied by appropri-
ate blanks. FRBs must remain hermetically sealed until
analysis.
8 3 2 Use the same procedures used for samples to add ascorbic acid
8-3 2 Sc? Unlinks (Sect. 8.1.1). The » batch of ascorbic
acid and HC1 should be used for the field reagent blanks in
the field.
9. QUALITY CONTROL
9 l Oualitv control (QC) requirements are the initial demonstration of
laboratory capability followed by regular analyses of la^™*°ry
reaaent blanks, field reagent blanks, and laboratory fortified
blanks. Each laboratory must maintain records to document the
quality of the data generated. Additional quality control practices
are recommended.
9 2 Initial demonstration of low system background. Before any samples
are analvzed it must be demonstrated that a laboratory rea9ent blank
(LRB) is reasonably free of contamination that would prevent the
determination of .Sy analyte of concern.Sources * background
contamination are glassware, purge level
Background contamination must be reduced to an acceptable level
S5S KS&Mi Mi KodI3er^'inn9roun
9 3 « srsiiStS ia^r?^7rarocrr?oyrt?^rebn^oco„t^!ynr
each analyte of concern at a concentration in the range of 0.2-5 pqfl
(see appropriate regulations and maximum contaminant levels for
guidance on appropriate concentrations).
9 3 1 Prepare each replicate by adding an appropriate aliquot of a
duality control sample to reagent water. If a qualitycon-
trol sample containing the method analytes is not available,
a primary dilution standard made from a source of reagents
different than those used to prepare the,cf11 5.1?« !ian~
dards may be used. Also add the £h
internal standard and surrogate compounds. J™1*" each
replicate according to the procedures described in Sect. 11,
and on a schedule that results in the analyses of all repli-
cates over a period of several days.
9 3 2 Calculate the measured concentration of each In each
replicate, the mean concentration of each analyte In all
replicates, and mean accuracy (as percentage of true
19
-------
9.3.3
9.3.*
9.4
value) for each analyte, and the precision (as relative
HJ5! wSia
tion described in Sect. 13.2 (3).
gasesand l!?Te?Ut1ng higher jjolecuUr .eight c«p.unds, »re
»ass^s§^7'-
^Tr^&Hs?£wS
nificant record of data quality.
Monitor the IntegrateI .re*j of
standards and surrogates (Tab ) reasonably constant
bratlon checks, and blanks, ines matrix effect or an
over time. A" ?^u^fC^^®"eMJliurface Is utilize* it «y
instrument pr°bl«. If » cry^enic the trao to the column. These
iirr»ws»»M7-'
sis s s*~ ffjasssy - -
problem must be found and corrected.
LABORATORY REAGENT BLAMS (J-jjB) J^Jze^LRB^rdetermine the
cessed as a group within a work shift, analyze in
background system contamination. A FRB (seci. »-/
place of a LRB.
sv^:>3s^ssa?£
SS'IS: ca' "eTbt.Ld If •^ATr^r^rl fStt.*
control
charts to document data quality.
9'7 a^y"^ $The°r.slns
9.5
20
-------
9.8
9.9
Hon resulting fro. fl.ld .
the FRB shows unacceptable contamination,
define the source of the Impurities.
SS38r-
S&«iSi«3SalS£&:
and correct the problem source.
•¦-asj.sa^Sj^HS'a^iS?
SS3SS£®3isrs ffWaa-
a-SryKsa wsai-sst
reported with them.
•" -srs sws&rrisrra: rsMwas
problems.
10. r*i TRB*TI0W W f^MnftRDIZATION
10.1 Demonstration and docu«nUt1on
required before any sables are analyzed »M is req cont1nu-
tently throughout sajple analys s as dlcutea^r ^ successful _ ,
SrtISHSa52rlSr«htchC5ntVyUsrt?e15e?fS™ed! b^1?lSn«l,'pS?lSr!!SdS?e aUd/o? SC conditions given j» Sect.11.
proceeding with calibration. An average spectrum across the
GC peak may be used to evaluate the performance of the sys-
tem.
10 2.3 Purge a medium CAL solution, (e.g., 10-20 jtg/L) using the
procedure given in Sect. 11.
21
-------
10.2.*
ass r
and ~ shown acceptable total Ion chrowtogrws.
10 2 4.1 6C perfomance. Sood colujn performan« «ill pro-
duci sy*»etr1cal peaks with °°st
compounds. If peaks »« «11les b«-
peaks are running together wlth 1»»111es be
tween theai, the wrong colian Ins been seiecteo or
reaedlal action Is probably necessary (Sect.10.3.6).
10 2 4 2 MS sensitivity. The 6C/HS/0S peak Identification
10.2.4.2 » sensiiivij^ ^ ,bU u rec09ni2, , « peak In
the appropriate retention t1«e window for McjJ
the cMoounds In calibration solution, and make
correct tentative identif1cJ^°5?^. ^ystS^lnte-
99% of the compounds are recognized, system ma
nance 1s required. See Sect. 10.3.6.
io-2-5 iffa:rr^Kttrh
GC/WS data syste. Xnlts used
tofe*pres$rqu»nt1t1es of analyte and Internal standard »ust
10.2.6
be equivalent.
RF. (AxXQu)
A,.
Q, •
(Ais) W»)
where: A, » Integrated abundance of the quantitation 1on
In'VrrtJdVbundance of the quantitation Ion
of the Internal standard,
quantity of analyte purged 1n nanograms or
concentration units,
quantity of Internal standard purged In ng or
concentration units.
standard deviation (SO) and the «nt1ve st>nd«rd
deviation (RSO) from each Bean. RSD - 100 (SD/H).
if ik. ocn of any analyte or surrogate mean Rr
exce^s^M, either analyze additional aligns of
aooroorlate CAL solutions to obtain an acceptable
SS of RFs over the entire concentration range, or
22
-------
take action to Improve 6C/HS performance Sect.
10.3.6). Surrogate compounds are present at the
same concentration on every sample, calibration
standard, and all types of blanks.
10 2.7 As an alternative to calculating mean response factors and
applying the RSD test, use the GC/HS data system software or
other available software to generate a linear or second order
regression calibration curve.
10.3 CONTINUING CALIBRATION CHECK ~ Verify the HS tune and Initial
calibration at the beginning of each 8-hr work shift during which
analyses are performed using the following procedure.
10.3.1 Introduce Into the GC (either by purging a laboratory reagent
blank or making a syringe injection) 25 ng or less of BFB and
acquire a mass spectrum that includes data for m/z 35-260.
If the spectrum does not meet all criteria (Table 3), the MS
must be retuned and adjusted to meet all criteria before
proceeding with the continuing calibration check.
10.3.2 Purge a medium concentration CAL solution and analyze with
the same conditions used during the initial calibration.
10.3.3 Demonstrate acceptable performance for the criteria shown in
Sect. 10.2.4.
10.3.4 Determine that the absolute areas of the quantitation ions of
the internal standard and surrogates have not decreased by
more than 30% from the areas measured in the most recent
continuing calibration check, or by more than 50% from the
areas measured during initial calibration. If these areas
have decreased by more than these amounts, adjustments must
be made to restore system sensitivity. These adjustments may
require cleaning of the MS ion source, or other maintenance
as indicated in Sect. 10.3.6, and recalibration. Control
charts are useful aids in documenting system sensitivity
changes.
10.3.5 Calculate the RF for each analyte of concern and surrogate
compound from the data measured in the continuing calibration
check. The RF for each analyte and surrogate must be within
30% of the mean value measured in the initial calibration.
Alternatively, 1f a linear or second order regression is
used, the concentration measured using the calibration curve
must be within 30% of the true value of the concentration in
the medium calibration solution. If these conditions do not
exist, remedial action must be taken which may require re-
calibration.
23
-------
io-3-6
qulrareturnlng to the Initial c»11br.t1on step.
as a tfs.&awasss'tffisr1
scale.
aw rsrws.swwr u
if XI"i.3«tl«i llMf H w >"< •' »*
system.
10.3.6.3 Flush the 6C coluw »Uh solvent »ccord1n9 to Mnu-
facturer's Instructions.
retention times. Analyst may need to redefine
retention windows.
10 3.6.5 Prepere fresh ML solutions, »nd repeit the Inltlil
calibration step.
10.3.6.6 Clean the MS ion source and rods (1f a quadrupole).
10 3 6 7 Replace any components that allow analyses to come
10.3.6.7 hot «etal surfaces, -
10.3.6.8 Replace the MS electron multiplier, or any other
faulty components.
fS S«l«»ks in tte pur,, mk tr.p unit as well «s
the rest of the analytical system.
io-4 ^u:4\rytbnir^o^5.,!:,Mu^rc1rr,;c^Viiieedd rr
following steps.
10.4.1 Fill ^e purging device with 25.0 ml (or 5-mL) of reagent
water or aqueous calibration standard.
10.4.2
tight syringe. Slowly Inject tne g«*o , *t 2000 M|_/«1n.
IfPthe
24
-------
sample Inlet port, flush the dead volwe with several mL of
room air or carrier gas. Inject the gaseous standard before
5 «1n of the 11-min purge time have elapsed.
10 4 3 Determine the aqueous equivalent concentration of vinyl
1 chloHde standard? In pg/L. injected -1th the equation:
S - 0.102 (C)(V)
where S ¦ Aqueous equivalent concentration
of vinyl chloride standard 1n /ig/L;
C ¦ Concentration of gaseous standard 1n mg/L (v/v);
V • Vol use of standard Injected in mL.
11. PROCEDURE
11.1 SAMPLE INTRODUCTION AND PURGING
11.1.1 This method 1s designed for a 25-mL sample v«lunie. but a
smaller (5 ml) sample volume Is recommended if the GC/MS
system has adequate sensitivity to achieve the required
method detection limits. Adjust the helium purge gas flow
rate to 40 mL/min. Attach the trap inlet to the purging
device and open the syringe valve on the purging device.
11.1.2 Remove the plungers from two 25-mL (or 5-mL depending on
sample size) syringes and attach a closed syringe valve to
each. Harm the sample to room temperature, open the sample
bottie, and carefully pour the sample into one of the syringe
barrels to just short of overflowing. Replace the syringe
plunger, Invert the syringe, and compress the sample. Open
the syringe valve and vent any residual air while adjusting
the sample volume to 25.0-mL (or 5-mL). To all samples,
blanks, and calibration standards, add 5-/iL (or an appropri-
ate volume) of the fortification solution containing the
internal standard and the surrogates to the sample through
the syringe valve. Close the valve. Fill the second syringe
in an identical manner from the same sample bottle. Reserve
this second syringe for a reanalysls if necessary.
11.1.3 Attach the sample syringe valve to the syringe valve °" JJ»e
purging device. Be sure that the trap is cooler than 25®C,
then open the sample syringe valve and inject the sample into
the purging chamber. Close both valves and initiate purging.
Purge the sample for 11.0 min at ambient temperature.
11.1.4 Standards and samples must be analyzed in exactly the same
manner. Room temperature changes 1n excess of 10 F may
adversely affect the accuracy and precision of the method.
25
-------
11.2.3
11.2 SAMPLE DESORPTION
ii9i Non-crvoaen1c interface - After the 11-min purge, place the
purge and trap system 1n the desorb mode and preheat the^trap
to 180°C without a flow of desorption gas. Then simultan-
eously start the flow of desorption gas at a
able for the column being used (optimum desorb flow rate is
15 mL/min) for about 4 min, begin the GC temperature program,
and start data acquisition.
11 2 2 Cryogenic interface - After the 11-min purge, place the
purge and trap system in the desorb mode, make sure the _
Scenic interface is a -150°C or lower, and rapidly heat
the trap to 180°C while backflushing with an inert gas at
~ mL/min for about 5 min. At the end of the 5 min
cycle rapidly heat the cryogenic trap to 250°C, and simulta-
neously begin the temperature program of the gas chromato-
graph, and start data acquisition.
While the trapped components are being introduced into the
gas chromatograph (or cryogenic interfacej.e^tythepurglng
dpvice usinq the sample syringe and wash the chwber with two
25-iL flushes of reagent water. After the purging device has
been enptled, leave syringe valve open to allow the purge gas
to vent through the sample Introduction needle.
s asuwiSfa?: ¦
overhead tt«e> of 2 sec or less. If "car^"
dioxide cause a background problen, start at 47 or 48 «/z. i
ketones are to be detemtned, data «ust be acquired starting at ./i
43 CvclHlie wist be adjusted to wasure five or »re spectra
during the elutlon of each 6C peak. Suggested temperature progra.s
are provided below. Alternative temperature programs can be used.
11 "j i c4f>flie rami linear temperature program for wide bore column 1
U and2with^ajetseparator. AdjuH the heliu. carrier gas
flow rate to within the capacity of the separator, or about
15 mL/min. The column temperature is reduced 10 C and held
for 5 min from the beginning of desorption, then programmed
to 160°C at 6°C/min, and held until all components have
eluted.
ii « 4 Multi-ramo temperature program for wide bore column 2 "ith
the open^plMMnterface. Adjust the heliu. carrier gas flow
rate to about 4.6 mL/min. The column temperature is reduced
to 10°C and held for 6 m1n from the beginning of desorption,
then heated to 70°C at 10°/min, heated to 120 C at 5 /min,
heated to 180° at 8°/m1n, and held at 180 until all com-
pounds have eluted.
26
-------
11.3.3 Single ramp linear temperature program for narrow bore column
3 with a cryogenic Interface. Adjust the helium carrier gas
flow rate to about 4 mL/m1n. The column temperature 1s
reduced to 10'C and held for 5 min from the beginning of
vaporization from the cryogenic trap, programmed at 6"/min
for 10 min, then 15*/imin for 5 min to 145*C, and held until
all components have eluted.
11.3.4 Multi-ramp temperature program for wide bore column 4 with
the open split interface. Adjust the helium carrier gas flow
rate to about 7.0 mL/m1n. The column temperature 1s - 10 C
and held for 6 min. from beginning of desorptlon, then heated
to 100*C at 10*C/min, heated to 200*C at 5'C/mln and held at
200"C for 8 min or until all compounds of Interest had elut-
ed.
11.4 TRAP RECONDITIONING — After desorbing the sample for 4 min, recondi-
tion the trap by returning the purge and trap system to the purge
mode. Halt 15 sec, then close the syringe valve on the purging
device to begin gas flow through the trap. Maintain the trap temper-
ature at 180®C. Maintain the moisture control module, If utilized,
at 90"C to remove residual water. After approximately 7 min, turn
off the trap heater and open the syringe valve to stop the gas flow
through the trap. When the trap 1s cool, the next sample can be
analyzed.
11.5 TERMINATION OF OATA ACQUISITION - When all the sample components
have eluted from the GC, terminate MS data acquisition. Use appro-
priate data output software to display full range mass spectra and
appropriate plots of ion abundance as a function of time. If any ion
abundance exceeds the system working range, dilute thesample aliquot
in the second syringe with reagent water and analyze the diluted
aliquot.
11.6 IDENTIFICATION OF ANALYTES — Identify a sample component by compari-
son of its mass spectrum (after background subtraction) to a refer-
ence spectrum in the user-created data base. The GC retention time
of the sample component should be within three standard deviations of
the mean retention time of the compound in the calibration mixture.
11.6.1 In general, all ions that are present above 10% relative
abundance in the mass spectrum of the standard should be
present in the mass spectrum of the sample component and
should agree within absolute 20%. For example, if an on has
a relative abundance of 30% 1n the standard spectrum, its
abundance 1n the sample spectrum should be In the range of 10
to 50%. Some ions, particularly the molecular 1on, are of
special importance, and should be evaluated even if they are
below 10% relative abundance.
11 6 2 Identification requires expert judgment when sample compo-
nents are not resolved chromatographically and produce mass
spectra containing ions contributed by more than one analyte.
27
-------
SCilSI?#
SiilsSlsg:.
sSll JjiecSus P?Suc» coS»r«tlv.ly s1«pl. spec-
f"1 thls^s wt » slgnlflct proble. for «ost «thod
tra,
analytes.
11.6.3
11.6.4
ti«?tiM
lace than 25% of the average height of the two peaKS. uvn
liU structural 1s«rs .re identify as H^rcp.ir;
_ '# it ilmAa itnapfic xvlenes ind two of the three di
gS-SE&SWEK.
bUnk froi the concentration 1n the sa«ple 1$ njt »««P*1'"e
because the concentration of the background 1n the blank 1s
highly variable.
12. m WYSIS m CAICVIATIQHS
121 '"
adequate Intensities are available for quantitation.
12.1.1 Calculate analyte and surrogate concentrations.
r _ (A.) Mi.) I000
" (A,.) RF * . , „
.here: C - concentration of analyte or surrogate 1n (ig/l
» , integrated Abundance of the quantitation Ion
A . In'^rlft^'Vi^ance'Vf th?
-------
12.1.2 Alternatively, use the GC/MS system software or other
available proven software to compute the concentrations of
the analytes and surrogates from the linear or second order
regression curves.
12.1.3 Calculations should utilize all available digits of precis-
Ion, but final reported concentrations should be rounded to
an appropriate number of significant figures (one digit of
uncertainty). Experience indicates that three significant
figures nay be used for concentrations above 99 /ig/L, two
significant figures for concentrations between 1- 99 pg/l,
and one significant figure for lower concentrations.
12.1.4 Calculate the total trlhalomethane concentration by summing
the four individual trlhalomethane concentrations.
13. mfthop performance
13.1 Single laboratory accuracy and precision data were obtained for the
method analytes using laboratory fortified blanks with analytes at
concentrations between 1 and 5 /ig/L. Results were obta ned using the
four columns specified (Sect. 6.3.2.1) and the open split or jet
separator (Sect. 6.3.3.1), or the cryogenic Interface (Sect.
6.3.3.2). These data are shown In Tables 4-8.
13.2 With these data, method detection limits were calculated using the
formula (3):
^ » 0.99)
where:
t, , , ,„K n ooi * Student's t value for the 99% confidence
. leyel n_j degrees of freedom,
n - number of replicates
S - the standard deviation of the
replicate analyses.
14. pnilliTTOM PREVENTION
14.1 Ho solvents are utilized in this method except the extremely small
volumes of methanol needed to make calibration standards. The only
other chemicals used In this method are the neat materials 1n prepar-
ing standards and sample preservatives. All are used in extremely
small amounts and pose no threat to the environment.
15. WASTE MANAGEMENT
15.1 There are no waste management Issues involved with this method. Due
to the nature of this method, the discarded samples are chemically
less contaminated than when they were collected.
29
-------
16. REFERENCES
1.
4.
5.
6.
7.
8.
ywr®
Ki^K-KXiriSS.1?«KB.SEttJB-M..
r h»4himi "Volatile Oraanlc Compounds in Hater by Purge and Trip
GC/HS • ProceedlSss of tht tUt.r Qu.llty Technology
C^re^ce iTric^ kter Sorrs Association. Denver, CO, Dece»b«r
1984.
J A Glaser, D.L. Foerst, G.O. McKee, S.A. Quave, and W.L. Budde,
¦Trace Analyses for Wastewaters, "Environ- Sfii- Ififiimfll-. IS. 14?6»
1981.
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
•OSHA Safety and Health Standards, eeneral 22o|9CfRevlsed
Occupational Safety and Health Administration, OSHA 2206, (Revised,
January 1976).
-Safety in Academic Chemistry Laboratories,' ^rican Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition,
1979.
R F Arrendale, R.F. Severson, and O.T. Chortyk, "Open Split
face for Capillary Gas Chromatography/Mass Spectrometry, Anal- Cfcsa-
1984, 54, 1533.
i i n«rh P S Fair "The Analysis of Cyanogen Chloride in Orink-
ina Water Proceedings of Water Quality Technology Conference,
AiwrtMn VUter Works Assoc)ation, St. Louis. HO., Novertor 14-16,
1988.
30
-------
17. Tim K. BIASMIBj nmiCHAPTS. HB VALIDATION DATA
TABLE 1. MOLECULAR HEIGHTS AND QUANTITATION IONS FOR NETHOO ANALYTES
Primary
Quantitation
Secondary
Quantitation
standard
F1uorobenzene 96 96 ^
Surrogates
4-Bromofluorobenzene 174 95 174,176
1,2-D1chlorobenzene-d4 150 152 lia.iau
TVget Anal vtes
cq 43 58
Acetone J; 53
Acrylonltrlle 53 bZ
Ally! chloride « 77
_ Benzene '» " 77jl58
Bromobenzene |»J }* 49,130
Broraochl oromethane 128 128 85 127
Bromodlchloromethane 162 83 175*252
Bromoform 250 i/J ' 96
Bromomethane '!! 57 70
2-Butanone " «
n-Butylbenzene JJ* «
sec-Butylbenzene 134 105 ^
tert-Butyl benzene 134 u»
Carbon disulfide 76 76
Carbon tetrachloride 152 117
Chloroacetonltrlle 75 48
Chl orobenzene 112 112
1-Chlorobutane 92 56
Chloroethane 64 64
Chloroform 118 g
Chloromethane 50 50
2-Chlorotoluene 126 91 J26
4-Chlorotoluene 126 91
Dibromochloromethane 206 __
1,2-01 bromo-3-Chloropropane 234 75 i».J
M-DlbrMoethme 86 107 109,188
Dtbromonethane l'| ®j[ 111*148
1.2-01 chl orobenzene 146 146 » }«
1.3-01chlorobenzene 146 }« 43
1.4-01chlorobenzene 146 146 »
31
-------
TABLE 1. (continued)
Primary
Quantitation
Secondary
Quantitation
trans-1,4-Di chl oro-2-butene 12* 53 .
Oi chlorodi f1uoromethane 120 g „
1.1-Oichloroethane 98 jg *98
1.2-Dichloroethane 98 m
1.1-DIchloroethene 96 96 *n
ci s-1,2-D1chloroethene 96 96
trans-1,2-Dichloroethene 96 96
1.2-D1chloropropane 1JZ 78
1.3-D1chloropropane JJZ 97
2,2-Di chl oropropane 1JZ " n0 77
1,1-Di chloropropene 110 75
1,1-01 chl oropropanone 126 *£ no
ci s-1,3-d 1 chl oropropene 110 no
trans-1,3-d1chloropropene 110 'J 45 n
Diethyl ether M \\ iM
Ethyl benzene }06 99
Ethyl methacrylate 11J 260
Hexachl orobutadl ene 258 2Q1
Hexachloroethane 23* U'm
2-Hexanone 9? 105 120
I sopropyl benzene 120 j w4 M
4-Isopropyltoluene 134 ..
Methacrylonitrlle 67 o ^
Methyl acrylate 86 w 86 49
Methylene chloride 84 84 .
Methyl iodide « ,,
Methyl methacryl ate 100 » 58,85
4-Methyl -2-pentanone 100 « »
Methyl-t-butyl ether 88
Naphthalene 128 128
Nitrobenzene ji
2-Nitropropane 89 119.167
Pentachl oroethane 200 11? " " ZL
Proplonitrlle 55 12Q
n-Propylbenzene 120 9} 7g
Styrene J 04 }»« 133 n9
1,1,1,2-Tetrachl oroethane 166 131
1,1,2,2-Tetrachloroethane 166 83 168 129
Tetrachloroethene 164 166 iw.izs
Tetrahydrofuran 72 71
Toluene 9Z .g.
1.2.3-Tr i chlorobenzene 180 180 j®'
1.2.4-Tr i chlorobenzene 180 180 1
1,1,1-Trlchloroethane 132 97 .
1,1,2-Trichloroethane
32
-------
TABLE 1. (continued)
Primary
Quantitation
Secondary
Quantitation
Trlchloroethene
Trlchlorofluoromethane
1.2.3-Tr1chloropropane
1.2.4-TrImethylbenzene
1.3.5-Trlmethylbenzene
Vinyl Chloride
o-Xylene
m-Xylene
p-Xylene
130
136
146
120
120
62
106
106
106
95
101
75
105
105
62
106
106
106
130,132
103
77
120
120
64
91
91
91
"Honolsotoplc molecular wight calculated fro* the ato. 1c nasses of the
Isotopes with the smallest masses.
33
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TABLE 2. CHROMATOGRAPHIC RETOfTlOJI TMB FOR K1M0 ANALYTES
ON THREE COLUMNS WITH FOUR SETS OF CONDITIONS
^omoount
Tptprnal standard
Fluorobenzene
Surrogates
4-Bromofluorobenzene
1,2-Di chlorobenzene-d4
Target Analvtes
Acetone
Acrylonitrlle
Allyl chloride
Benzene
Bronobenzene
Bromochloromethane
Bromodichloromethane
Bronioform
Bromomethane
2-Butanone
n-Butylbenzene
sec-Butyl benzene
tert-Butylbenzene
Carbon Disulfide
Carbon Tetrachloride
Chloroaceton1tr1le
Chlorobenzene
1-Chlorobutane
Chloroethane
Chloroform
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
Cyanogen chloride (8)
01bromochloromethane
1,2-Dibromo-3-Chloropropane
1,2-Oibromoethane
01 bromomethane
1.2-01chlorobenzene
1.3-01chlorobenzene
1.4-01chlorobenzene
t-1,4-D1chloro-2-butene
D1chlorodi f1uoromethane
1,1-01chloroethane
Retention . Time (minrsec)
8:49
18:38
22:16
6:27
15:43
19:08
8:14
5:40
18:57
15:52
6:44
4:23
10:35
8:29
17:56
14:53
2:01
0:58
22:13
19:29
20:47
18:05
20:17
17:34
7:37
5:16
15:46
13:01
2:05
1:01
6:24
4:48
1:38
0:44
19:20
16:25
19:30
16:43
14:23
11:51
24:32
21:05
14:44
11:50
10:39
7:56
22:31
19:10
21:13
18:08
21:33
18:23
1:33
0:42
4:51
2:56
14:06
23:38
27:25
8:03
)lumn 4'
22:00
31:21
35:51
16:14
17:49
16:58
13:30
7:25
21:32
24:00
16:25
31:52
12:22
5:38
20:20
15:48
9:20
23:36
22:46
15:42
30:32
4:48
1:17
12:26
19:41
27:32
17:57
35:41
26:08
17:28
34:04
25:36
17:19
33:26
16:30
13:10
7:25
21:11
23:51
20:40
14:20
28:26
21:00
1:27
12:36
5:33
20:27
3:24
0:58
9:11
24:32
16:44
32:21
24:46
16:49
32:38
1:03
19:12
12:48
26:57
18:02
38:20
19:24
13:36
27:19
15:26
9:05
23:22
27:26
17:47
35:55
26:22
17:28
34:31
26:36
17:38
34:45
31:44
3:08
0:53
7:16
10:48
4:02
18:46
34
-------
TABLE 2. (continued)
Retention
Time (min:sec)
luinn
r>>
1,2-Oichloroethane
1.1-Dichloroethene
ci s-1,2-0i chloroethene
trans-1,2-Di chloroethene
1.2-Dichloropropane
1.3-Dichloropropane
2,2-Dichloropropane
1,1-Di chloropropanone
1,1-Dichloropropene
cis-l,3-dichloropropene
trans-1,3-di chloropropene
Diethyl ether
Ethyl benzene
Ethyl Hethacrylate
Hexachlorobutadi ene
Hexachloroethane
Hexanone
Isopropylbenzene
4-Isopropyltoluene
Methacrylonitrile
Methylacrylate
Methylene Chloride
Methyl Iodide
Methylmethacrylate
4-Methyl-2-pentanone
Methyl-t-butyl ether
Naphthalene
Nitrobenzene
2-Nitropropane
Pentachloroethane
Propionitrile
n-Propylbenzene
Styrene
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Tetrahydrofuran
Toluene
1.2.3-Tri chlorobenzene
1.2.4-Tri chlorobenzene
1.1.1-Trlchloroethane
1.1.2-Trichloroethane
Trichloroethene
Tri chlorof1uoromethane
1.2.3-Tr1chloropropane
1.2.4-Trimethylbenzene
8:24
2:53
6:11
3:59
10:05
14:02
6:01
7:49
11.58
13.46
15:59
26:59
18:04
21:12
3:36
27:10
19:04
17:19
15:56
18:43
13:44
12:26
27:47
26:33
7:16
13:25
9:35
2:16
19:01
20:20
5:50
1:34
3:54
2:22
7:40
11:19
3:48
5:17
13:23
23:41
15:28
18:31
2:04
23:31
16:25
14:36
13:20
16:21
11:09
10:00
24:11
23:05
4:50
11:03
7:16
1:11
16:14
17:42
13:38
7:50
11:56
9:54
15:12
18:42
11:52
13:06
16:42
17:54
21:00
32:04
23:18
26:30
9:16
32:12
24:20
22:24
20:52
24:04
18:36
17:24
32:58
31:30
12:50
18:18
14:48
6:12
24:08
31:30
7:00
2:20
5:04
3:32
8:56
12:29
5:19
7:10
14:44
19:14
16:25
17:38
2:40
19:04
16:49
15:47
14:44
15:47
13:12
11:31
19:14
18:50
6:46
11:59
9:01
1:46
16:16
17:19
21:31
16:01
19:53
17:54
23:08
26:23
19:54
24:52
21:08
24:24
25:33
15:31
28:37
25:35
42:03
36:45
26:23
30:52
34:27
20:15
20:02
17:18
16:21
23:08
24:38
17:56
42:29
39:02
23:58
33:33
19:58
32:00
29:57
28:35
31:35
26:27
20:26
25:13
43:31
41:26
20:51
25:59
22:42
14:18
31:47
33:33
35
-------
TABLE 2. (continued)
Retention
(¦In:see)
?d Colin 4*
1,3,5-Tr imethylbenzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
19:28
1:43
17:07
16:10
16:07
16:54
0:47
14:31
13:41
13:41
24:50
3:56
22:16
21:22
21:18
16:59
1:02
15:47
15:18
15:18
32:26
10:22
29:56
28:53
28:53
hGC conditions given in Sect. 11.3.1.
eGC conditions given In Sect. 11.3.2.
<»GC conditions given in Sect. 11.3.3.
*GC conditions given in Sect. 11.3.4.
36
-------
TABLE 3. ION ABUNDANCE CRITERIA FOR 4-BROHOFLUOROBENZENE (BFB)
Mass
fH/zl polative Abundance Criteria
50 15 to 4OX of mass 95
75 30 to 80% of mass 95
gc Base Peak, 100% Relative Abundance
96 5 to 9% of mass 95
173 < 2% of mass 174
174 > 50% of mass 95
175 5 to 9% of Bass 174
176 > 95% but < 101% of mass 174
177 5 to 9% of mass 176
37
-------
Tioi c a iCfllRACY AND PRECISION DATA FROM 16-31 DETERMINATIONS OF THE HETHOO
«• AceuwtY MB USIHG WK |0M WIIU„ COLUW 1*
Compound
True Hem R®1 • Method
Std. Det.
Dev. Limit
f*> fq/n
Cone.
Range
fua/H
Accuracy
(X of True
Value!
0.1-10
97
0.1-10
100
0.5-10
90
0.1-10
95
0.5-10
101
0.5-10
95
0.5-10
100
0.5-10
100
0.5-10
102
0.5-10
84
0.1-10
98
0.5-10
89
0.5-10
90
0.5-10
93
0.1-10
90
0.1-10
99
0.1-10
92
0.5-10
83
0.5-10
102
0.5-10
100
0.1-10
93
0.5-10
99
0.2-20
103
0.5-10
90
0.5-10
96
0.1-10
95
0.1-10
94
0.5-10
101
0.1-10
93
0.1-10
97
0.1-10
96
0.5-10
86
0.5-10
98
0.1-10
99
0.5-10
100
0.5-10
101
0.1-10
99
0.1-10
95
0.1-100
104
0.1-10
100
0.1-100
102
s=— 5-i:» '1 s| S
Bromochlororaethane 5*?"}2 oc si 0 08
Bromodichloromethane 0.1-10 95 6.1 o.
Bromofonn 0.5-0 101 6.3 0.1Z
Bromomethane inn 7*6 0 11
n-Butylbenzene 0.5-10 100 7.6 .
sec-Butyl benzene 0.5-10 100 7.6 .
tert-Butylbenzene 0.5-10 102 7.3 .
Carbon tetrachloride 0.5-10 84 . •
Chlorobenzene 0.1-0 98 5.9 o.uj
Chloroethane £*!~}X on 61 0 03
Chloroform 0.5- 0 90 6.1 0.03
Chioromethane 0.5-10 93 8. .
2-Chlorotoluene 0.1-10 90 6.2 0.04
4-Chlorotoluene 0.1-10 99 8.3 0.0b
Dibromochloromethane 51"!2 J? io"g o 26
1,2-0ibromo-3-chloropropane 0.5-10 83 19.9
1,2-Oibromoethane 0.5-10 102 3-J j-wj
lf3-0ichlorobenzene 0.5-10 99 o.* .
1,4-D1chlorobenzene 0,2"?2 2* 77 n'10
Dibromomethane 0.5-10 100 a. ¦
1,2-DIchlorobenzene 0.1-10 93 6.2
6.4 0.03
Dichlorodifluoromethane ?? 0*04
1.1-D1chloroethane 0.5- 0 96 5.3 0.0«
1.2-01chloroethane |5 6 7 0'u
1.1-01chloroethene 2*J~}2 ij? 1*7 0 12
cis-1,2 Dichloroethene 0.5-10 101 6.7 o.
trans-1,2-Di chloroethene 0.1-10 93 5.6 0.
1.2-D1chloropropane 0.1-10 97 6.1 0.04
1.3-Dichloropropane 0.1-10 96 6.0 .
2,2-Di chl oropropane 0.5- 0 86 16.9 0.35
1,1-Dlchloropropene 0.5-10 98 8.9
ci s-1,2-Di chloropropene
trans-1,2-Dichloropropene Q6
Ethyl benzene 0.1-10 99 8.6 0.06
Hexachlorobutadi ene 0.5-10 100 6.8 0.11
Isopropylbenzene 0.5-10 101 7.6 0. 5
4-1 sopropy 1 tol uene ?? 1*3 003
Methylene chloride 0.1-10 95 5.3 0.03
Naphthalene 0.1-00 04 8.2 0.04
StyrenelbenZ6ne 102 7*J o'.SJ
38
-------
TABLE 4. (Continued)
Compound
True
Cone.
Range
(M/l)
Mean
Accuracy
(% of True
Valued
Rel.
Std.
Dev.
Method
Det.
Limit
ili q/L)
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1.2.3-Tri chlorobenzene
1.2.4-Tr i chlorobenzene
1.1.1-Trichloroethane
1.1.2-Trichloroethane
Trichloroethene
Tri chlorofluoromethane
1.2.3-Tri chloropropane
1.2.4-Trimethylbenzene
1.3.5-Trimethylbenzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
0.5-10
0.1-10
0.5-10
0.5-10
0.5-10
0.5-10
0.5-10
0.5-10
0.5-10
0.5-10
0.5-10
0.5-10
0.5-10
0.5-10
0.1-31
0.1-10
0.5-10
90
91
89
102
109
108
98
104
90
89
108
99
92
98
103
97
104
6.8
6.3
6.8
8.0
8.6
8.3
8.1
7.3
7.3
8.1
14.4
8.1
7.4
6.7
7.2
6.5
7.7
0.05
0.04
0.14
0.11
0.03
0.04
0.08
0.10
0.19
0.08
0.32
0.13
0.05
0.17
0.11
0.05
0.13
'Data obtained by using column 1 with a jet separator interface and a
quadrupole mass spectrometer (Sect. 11.3.1) with analytes divided among
three solutions.
Replicate samples at the lowest concentration listed in column 2 of this
table were analyzed. These results were used to calculate MDLs.
39
-------
TABLE S.
SSSS
MID A NARROW BORE CAPILLARY COLUMN 3*
True
Cone.
Mean
Accuracy
(% of True
Rel. Method
Std. Dect.
Dev. Llilt
Benzene
ironobenzene
roaochloromethane
iroaodlchloroaethane
trooofom
iromonethane
-Butylbenzene
iec-Butylbenzene
tert-Butylbenzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
thlorofom
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
Cyanogen chloride
D1bronochloroaethane
1,2-01 bromo-3-chloropropane
1,2-01bromoethane
Olbromomethane
1.2-01chlorobenzene
1.3-01chlorobenzene
1.4-01chlorobenzene
D1chlorod1f1uoromethane
1.1-01chloroethane
1.2-01chloroethane
1.1-01chloroethene
c1s-l,2 01chloroethene
tran s-1,2-D1chloroethene
1.2-01chloropropane
1.3-01chloropropane
2,2-01chloropropane
l,l-D1chloropropene
c1s-l,3-01chloropropene
trans-1,3-01chloropropene
Ethylbenzene
Hexachlorobutad1ene
Isopropylbenzene
4-Isopropy1toluene
Methylene chloride
Naphthalene
0.1
99
0.5
97
0.5
97
0.1
100
0.1
99
0.1
99
0.5
94
0.5
90
0.5
90
0.1
92
0.1
91
0.1
100
0.1
95
0.1
99
0.1
99
0.1
96
92
0.1
99
0.1
92
0.1
97
0.1
93
0.1
97
0.1
99
0.1
93
0.1
99
0.1
98
0.1
100
0.1
95
0.1
100
0.1
98
0.1
96
0.1
99
0.1
99
0.1
98
0.1
99
0.1
100
0.5
98
0.5
87
0.5
97
0.1
98
6.2
7.4
5.8
4.6
5.4
7.1
6.0
7.1
2.5
6.8
5.8
5.8
3.2
4.7
4.6
7.0
10.6
5.6
10.0
5.6
6.9
3.5
6.0
5.7
8.8
6.2
6.3
9.0
3.7
7.2
6.0
5.8
4.9
7.4
5.2
6.7
6.4
13.0
13.0
7.2
0.03
0.11
0.07
0.03
0.20
0.06
0.03
0.12
0.33
0.08
0.03
0.02
0.02
0.05
0.05
0.05
0.30
0.07
0.05
0.02
0.03
0.05
0.05
0.04
0.11
0.03
0.02
0.05
0.06
0.03
0.02
0.04
0.05
0.02
0.03
0.04
0.10
0.26
0.09
0.04
40
-------
TABLE 5. (Continued)
True
Cone.
Mean
Accuracy
(% of True
Rel. Method
Std. Dect.
Dev. Limit
n-Propyl benzene
Styrene
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
To!uene
1.2.3-Tr1chlorobenzene
1.2.4-Tri chlorobenzene
1.1.1-Trlchloroethane
1.1.2-Trichloroethane
Trichloroethene
Tr1chlorof1uoromethane
1.2.3-Tr1chloropropane
1.2.4-Tr1methylbenzene
1.3.5-Tri methylbenzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
0.1
99
0.1
96
0.1
100
0.5
100
0.1
96
0.1
100
0.1
98
0.1
91
0.1
100
0.1
98
0.1
96
0.1
97
0.1
96
0.1
96
0.1
99
0.1
96
0.1
94
0.1
94
0.1
97
6.6
19.0
4.7
12.0
5.0
5.9
8.9
16.0
4.0
4.9
2.0
4.6
6.5
6.5
4.2
0.2
7.5
4.6
6.1
0.06
0.06
0.04
0.20
0.05
0.08
0.04
0.20
0.04
0.03
0.02
0.07
0.03
0.04
0.02
0.04
0.06
0.03
0.06
"Data obtained by using column 3 with a cryogenic interface and a
quadrupole mass spectrometer (Sect 11.3.3)r
"•Reference 8.
G
41
-------
tari F 6 ACCURACY AND PRECISION DATA FROM SEVEN DETERMINATIONS
«• rn MW.YTES IK REA6EKT HATER USIMS HIDE SORE
CAPILLARY COLUMN 2*
Compound
No.b
Mean Accuracy
(% of True
Value, RSD
I iio/L Cone.) LSI-
Mean Accuracy
(% of True
Value, RSD
0 7 iio/L Cone.)—(£1
internal Standard
Fluorobenzene 1
Surrogates
4-Bromof 1 uorobenzene 2 98 1.8 96 1.3
l,2-Dichlorobenzene-d4 * 97 3,2
Target Analvtes
3/ */ -r.-r 113 1-8
5enze"e U 1S2 3.0 101 1.9
Bromobenzene 38 loz J.u ;•
Bromochl oromethane 4 99 5.2 1 •
Bromod i chl oromethane 5 96 1.8 1 ^
Br-omofGrm « » <; 52 6;7
Bromomethane 7 » «'• . 3
n-Butyl benzene 39 89 4.8 •
sec-Butyl benzene 40 102 3.5 1 2 9
tert-Butylbenzene 41 101 4.5 100 2 6
Carbon tetrachloride 8 .84 3.2 9Z z.o
2
98
1.8
3
97
3.2
37
97
4.4
38
102
3.0
4
99
5.2
5
96
1.8
6
89
2.4
7
55
27.
39
89
4.8
40
102
3.5
41
101
4.5
8
84
3.2
42
104
3.1
9
97
2.0
10
110
5.0
43
91
2.4
44
89
2.0
11
95
2.7
ec
13
99
2.1
45
93
2.7
46
100
4.0
47
98
4.1
14
38
25.
15
97
2.3
16
102
3.8
17
90
2.2
18
100
3.4
19
92
2.1
Chlorobenzene
Chloroethane6 n 0c ? 1
Chlorofon. 9 97 2.0 95 Z.l
Chloromethane 10 110 5.0
2-Chlorotoluene 43 91 2.4 108 3.1
4-Chlorotoluene 44 89 2.0 08 4.4
Dibromochloromethane 11 95 2.7
1,2-Di bromo-3-chloropropane
l,2-Dibromoethanec Q. - -
Dibromomethane 13 99 2.1 •
1.2-Di chlorobenzene 45 93 2.7 94 .
1.3-Di chlorobenzene 46 100 4.0 87 Z.
1.4-Dichlorobenzene 47 98 4.1 94
Dichlorodifluoromethane 14 38 z&. a
1.1-Dichloroethane 15 97 2.3 85 3.6
1.2-Di chl oroethane 16 102 3.8 100 .
1,1-Dichloroethene 17 90 2.2 87 3.8
cis-l,2-Dichloroethene 18 100 3.4 89 .
trans-l,2-Dichloroethene 1Q 92 2.1 8b
42
-------
TABLE 6. (Continued)
Compound
Mean Accuracy Mean Accuracy
(X of True <* True
Value, "SO Value, RSO
> 1 iia/l Conc.l til 0.? IM/l Cm,) m
1.2-01 chl oropropane 20 102 11 ff
1.3-01chloropropane 21
2,2-Dichloropropane
1,1-01chloropropene
ci s-1,3-Di chl oropropene 99 2A
trans-1,3-01 chloropropene 25 96 1.7 ^ 4 Q
Ethyl benzene JJ 96 |.t 2 4
Hexachlorobutadi ene 26 91 • m 2 j
I sopropyl benzene 49 103 . 9J 3 j
4-Isopropyltoluene 50 95 J-o
Methylene chloride 27 e 3
Naphtha ene 51 93 7.6 97 2^
n-Propyl benzene 52 102 ^ JQ4 3 A
1JU 1^2-Tetrachl oroethane 28 99 2.7 95 3.8
1,1,2,2-Tetrachloroethane 29 101 4.6 ^ ^
Tetrachloroethene 30 97 . m UJ
Toluene *4 R 7 78 2 9
1.2.3-Trlchlorobenzene 55 90 5.7
1.2.4-Trlchlorobenzene 56 9Z a* j .
1.1.1-Trichloroethane 31 94 3.9 ^
1.1.2-Tn chl oroethane 32 107 3.4 ^ 2 5
Trichloroethene 33 99 • ^
Trichlorofluoromethane 34 81 • . g
1.2.3-Tr1chloropropane 35 9/ 2*2
1 ^ 4-Trl methyl benzene 57 93 3 1 106 t.t
1.3.5-Trimethyl benzene 58 88 Z.4
Vinyl chloride g \\ ,.7
o-Xylene f
!? g8 2.J 103 1.4
p-Xylene 61
•Data obtained using column 2 with the open split Interface and an Ion
trap mass spectrometer (Sect. 11.3.2) with all »ethod analytes In the sane
reagent water solution.
''Designation 1n Figures 1 and 2.
cMot measured; authentic standards were not available.
Ttot measured ^methyl ene chloride was in the laboratory reagent blank,
'¦-xylene coelutes with and cannot be distinguished from its isomer p-xylene,
No 61.
Kj
43
-------
Tioi r 7 *rnIBICY AND PRECISION DATA FRON SEVEN DETERMINATIONS
™LE 7' wSmTO™ REA6EKT WATE* USIK6 HIDE BORE
CAPILLARY COLUMN 4
Compound
True
Cone.
(W/L)
Mean
Cone.
Oetected
(ug/L)
Rel
Std.
Dev.
(*)
Method
Det.
Unit
(M9/L)
Acetone
Acrylonitrlle
Ally! chloride
2-Butanone
Carbon disulfide
Chioroacetoni tr11e
1-Chlorobutane
t-1,2-D1chloro-2-butene
1,1-D1chloropropanone
Diethyl ether
Ethyl roethacrylate
Hexachloroethane
2-Hexanone
Methacrylonltrlle
Methylacrylate
Methyl iodide
Methylmethacrylate
4-Methyl-2-pentanone
Methyl-tert-butylether
Nitrobenzene
2-Nitropropane
Pentachloroethane
Propionitrile
Tetrahydrofuran
1.0
1.0
1.0
2.0
0.20
1.0
1.0
1.0
5.0
1.0
0.20
0.20
1.0
1.0
1.0
0.20
1.0
0.40
0.40
2.0
1.0
0.20
1.0
5.0
1.6
0.81
0.90
2.7
0.19
0.83
0.87
1.3
4.2
0.92
0.23
0.18
1.1
0.92
1.2
0.19
1.0
0.56
0.52
2.1
0.83
0.23
0.87
3.9
5.7%
8.7%
4.7%
5.6%
15%
4.7%
6.6%
8.7%
7.7%
9.5%
3.9%
10%
12%
4.2%
12%
3.1%
13%
9.7%
5.6%
18%
6.2%
20%
5.3%
13%
0.28
0.22
0.13
0.48
0.093
0.12
0.18
0.36
1.0
0.28
0.028
0.057
0.39
0.12
0.45
0.019
0.43
0.17
0.090
1.2
0.16
0.14
0.14
1.6
44
-------
o
TABLE 8.
•SSS.VSS'SlSSg.'SggST^J^'
REAGENT MATER
RAM WATER
TAP WATER
Compound
Mean
(Mfl/L)
Dev. (X of True Mean
(%) Value) (W/U
Oev. (* of True H»» 0«».
(X) Value) (WA) W
(X of True
Value)
Acetone
Acrylonltrlle
Allyl chloride
2-Butanone
Carbon disulfide
Chloroacetonitrlle
1-Chlorobutane
t-1,2-01chloro-2-butene
1,i-Oichloropropanone
01ethyl ether
Ethyl aethacrylate
Hexachloroethane
2-Hexanone
Methacrylonltrlle
Methylacrylate
19
20
20
17
19
20
18
19
20
18
20
20
19
20
20
12%
4.7%
5.1%
11%
6.4%
4.1%
6.4%
4.1%
S.6%
6.7%
3.7%
6.1%
6.3%
3.4%
3.7%
95%
100%
100%
85%
95%
100%
90%
95%
100%
90%
100%
100%
95%
100%
100%
21
22
20
19
18
23
19
22
22
22
23
21
21
23
22
3.7%
3.4%
2.8%
7.3%
2.5%
4.7%
2.2%
2.9%
6.4%
3.4%
2.6%
2.5%
3.8%
2.9%
3.1%
105%
110%
100%
95%
90%
115%
95%
110%
110%
110%
115%
105%
105%
115%
110%
22
21
19
17
18
23
17
21
21
22
22
21
21
22
21
8.2%
1.3%
3.5%
5.6%
3.0%
1.3%
2.2%
0.90%
7.7%
2.6%
1.8%
2.0%
4.0%
2.0%
2.1%
110%
105%
95%
85%
90%
115%
85%
105%
105%
110%
110%
105%
105%
110%
105%
-------
TABLE 8 (Continued)
REAGENT MATER
Compound
Methyl Iodide
Methylaethacrylate
4-Hethyl-2-pentanone
Methyl-tert-butylether
Nitrobenzene
2-N1tropropane
Pentachloroethane
Proplonltrlle
Tetrahydrofuran
Mean
(M9/U
20
20
19
19
20
20
19
20
20
Oev.
(X)
(X of True Mean
Value) (W/L)
4.4%
3.7*
8.7%
3.5%
5.4%
6.1%
5.2%
4.5%
2.8%
100%
100%
95%
95%
100%
100%
95%
100%
100%
19
23
21
22
22
23
21
23
24
RAM MATER
Dev. (% of True Hean
(%) Value) (Ml/*-)
3.8%
3.3%
5.5%
2.5%
4.8%
5.1%
2.6%
3.9%
3.2%
95%
115%
105%
110%
110%
115%
105%
115%
120%
TAP MATER
Oev. (% of True
(%) Value)
19
23
22
22
21
22
22
23
21
3.0%
2.7%
7.2%
3.6%
2.4%
3.2%
1.7%
2.4%
2.9%
95%
115%
110%
110%
105%
110%
110%
115%
105%
-------
c
MAY SVVNGC VALV1
HOL 20 GAUGE SIHNGE NCEDU
O.O.MJttStOTU*
1/wm.o.D.
STAMLESS STHL
10M1 GLASS
naiuii pomsm
uxnoticuuui
SIM PURGE
GASRLTB
PUtGEGAS
IRJOV
ICONmOL
FIGURE 1. PURGING DEVICE
O
47
-------
MOQNGnOCSMI
coNsmjcnoN
&
ACTWATB,
QXAOCK ,,,
8UCA (SB.
leiAI 7J
*0*1 1CJ
7A/VOOT
KSSTANCf
fUglMffO
M(JO<
(pouEium
iiau,
7WFOOT-.
ttSSTAMCt
VUCWMTO
KXJO
(SINGLE UYO)
MLST
TUVNG2SCM
1.101 M. U).
MS M. OA
ftJUNLBSflffl.
srsass;""""
48
-------
c
J. NOKMALIZSD TOTAL SON
<5 vt/L) Or NOCT OONVOtMM.
CMR0MATOCBAM HUM A VQU il OMfOUMD CALIBRATION MXTUIS CONTAINDK
THS COMPOUND IDCHTIFICATIOH NIMBUS All OIVW IN TABLl 6.
» N
-------
new 4.
TABU i.
ssasst swwbmse •srss.rsuss ssrrsss
w>
O
-------
METHOD 200.8
DETERMINATION OF TRACE ELEMENTS IN MATERS AND WASTES
BY INDUCTIVELY COUPLED PLASMA - MASS SPECTROMETRY
Stephen E. Long
Technology Applications, Inc.
and
Theodore D. Martin
Inorganic Chemistry Branch
Chemistry Research Division
Revision 4.4
April 1991
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
83
-------
METHOD 200.8
determination of TMCEELEHEKTS »IWTERS.«» «^ES
BY IHOUCTIVELY COUPLED PLASMA - MASS SPcCTROHt kt
1. Slflff W APPLICATION
1.1 This method provides procedures for deteralnation^of^issoWed ^
elements in ground waters, ?urfac total recoverable element
^".Uonll/Lfe^rrfas «ste«ters, sludges and
solid waste samples.
1.2 Dissolved elements are u
preservation. Acid digestion procedures are requ^ w
js u —
0.2% (w/v) (Sect. 4.1.4).
1.3 This method 1s applicable to the following elements:
Element
Aluminum (Al)
Antimony (Sb)
Arsenic (As)
Barium (Ba)
Beryllium (Be)
Cadmium (Cd)
Chromium (Cr)
Cobalt (Co)
Copper (Cu)
Lead (Pb)
Manganese (Mn)
Molybdenum (Mo)
Nickel (Ni)
Selenium (Se)
Silver (Ag)
Thallium (Tl)
Thorium (Th)
Uranium (U)
Vanadium (V)
Zinc (Zn)
Chemical Abstract Services
Registry Nirabers (CASRH)
7429-90-5
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-3
7440-48-4
7440-50-8
7439-92-1
7439-96-5
7439-98-7
7440-02-0
7782-49-2
7440-22-4
7440-28-0
7440-29-1
7440-61-1
7440-62-2
7440-66-6
Estimated Instrument detection
listed in Table 1. These are multielement determinations
limits typical of a system optimzed for netpui1zat1on
t^rl^^uarn^'le'rrtStVmethod detection limits (HOLs)
84
-------
and linear working ring" »"< •» dependent on the sample matrix,
instrumentation and selected operating conditions.
1.4 This method ts suitable for the determination of silver In aqueous
samples containing concentrations up to 0.1 mg/L. For tne analysis
o/wastewater samples containing higher concentrations of silver,
succeeding smaller volume, well mixed sample aliquots must be
prepared until the analysis solution contains < 0.1 mg/L silver.
1 5 This method should be used by analysts experlenced ln the use of
inHurtivelv couoled plasma mass spectrometry (ICP-MS), the
1nteroretat1on of spectral and matrix interferences and procedures
for their correction. A minimum of six months experience with
commercial instrumentation 1s recowended.
OF METHOD
9 l The method describes the multi-element determination of trace
elements by ICP-MS . Sample material in solution is introduced by
pneumatic nebulization into a radiofrequency P]a^
transfer processes cause desolvatlon, "S ? -.tjS-lSIlifli12 "
Th® innt are extracted from the plasma through a differentially
pumped vacuum interface and separated on the basis of
charge ratio by a quadrupole mass spectrometer having a minimum
resolution caoability of 1 amu peak width at 5% peak height. The
ions transmitted through the quadrupole are registered by a con-
tinuous dynode electron multiplier or Far®day detectlon
information processed by a data handling system. Interferences
relatTna to the technique (Sect. 4) must be recognized and corrected
for Such corrections must include compensation for
eleiental Interferences and '"teffej^nces fro» poly»t«1c Ions
derived from the plasma gas, reagents or sample matrix, insirumen
tal drift as well as suppressions or enhancements of ^n|^ru®Jen^.
response caused by the SSmple ««tr1x mist be corrected for by the
use of internal standardization.
DEFINITIONS
3.1 DISSOLVED - Material that will pass through a 0.45 fin membrane
filter assembly, prior to sample acidification.
3 2 TOTAL RECOVERABLE - The concentration of analyte determined on an
unflltered sample following treatment with hot dilute mineral acid.
¦» * tuktbijmfnt DETECTION LIMIT (IDL) - The concentration equivalent of
the analvtesiqnal which 1s eqial to three times the standard
deviation of the blank signal at the selected analytical mass(es).
3 4 METH00 DETECTION LIMIT (MDL) - The minimum concentration of an
analyte that can be identified, measured and reported with 99%
confidence that the analyte concentration is greater than zero.
85
-------
3.5
3.6
3.7
3.8
LINEAR DYNAMIC RANGE (LOR) - The concentratt°n range over «h1ch the
analytical working curve remains linear.
LABORATORY REAGENT BLANK (LM) (prepjr.tionsbUnk)
Jollfl^e! equ1pnent, soWents^j*eagents| in
-------
4. JMTERFERENCES
4.1 Several Interference sources jay cause th*
determination of trace elements by ICP-MS. These are.
4.1.1 Isobarlc elemental Interferences - Are c;usjJMbJ. JjjW*
different elements which form singly or doubly charged l^s
of the same nominal mass-to-charge ratio *
resolved by the mass spectrometer 1n use. All elements
determined by this method have, at a minimum, one .
free of Isobaric elemental int®^er®"ce* onlv
isotopes recommended for use with this Method £TjjJJe only
nolvbdenum-98 (ruthenium) and selenlum-82 (krypton) have
isobarlc elemental Interferences. If alternative *"*W1ca1
isotopes having higher natural abundance }JJ»J1Jcted lB
order to achieve greater sensitivity, an isobarlc
interference may occur. All data obtained under such condl-
tionsmust be corrected by measuring the signal from another
isotope of the interfering element and subtract1ng the
appropriate signal ratio from the Isotope the
record of this correction process should be Incliwed with the
report of the data. It should be noted thJttJ"cJ
will only be as accurate as the accuracy of the isotope ratio
used in the elemental equation for datacaleulaJ1°"s•. .. .
Relevant Isotope ratios and instrument bias factors should be
established prior to the application of any corrections.
4 i o AhnnHanre sensitivitv - Is a property defining the degree to
which the wings of a mass peak contribute to adjacent masses.
The abundance sensitivity Is affected by ion energy and quad-
rupole operating pressure. Wing overlap ^n^e|]^e*!®nces.^
result when a small ion peak is being measured adjacent to a
large one. The potential for these jni®rfer®"ce?J;hJ"ld be
recognized and the spectrometer resolution adjusted to
minimize them.
a l i Isobaric oolvatomic ion interferences - Are caused by ions
consisting of more than one atom which have the same
mass-to-charge ratio as the isotope of Interest, and which
cannot be resolved by the mass spectrometer in use. These
ions are commonly formed In the plasma or ^?r£!c®h*y*J?JL
from support gases or sample components. Most of the common
interferences have been identified , and these are ^sted in
Table 2 together with the method elements afJect®^-
interferences must be recognized, and when they cannot be
avoided by the selection of alternative anaWJ"1
appropriate corrections must be made t0* S?i I ?|Ii
for the correction of data should be established at the time
of the analytical run sequence as the polyatomic ion
interferences will be highly dependent on the sample matrix
and chosen instrument conditions.
87
-------
a i a Physical Interferences - Are associated with the physical
414 processes which govern the transport of » ;i Into the
olasma, sample conversion processes In the plasma, ana ine
SSSAirsS3WTB5S^5 TlSTsT-^SSti*
~Ko transfer of solution to the nebulizer (e.g., viscosity
iritUirved^tdt'^'Cs^iS eTco,™. <«•». ^
rftf:c^fveo2,«ufrfc^re^^reSs^^ecrrf";foc,,,9
transmission. Dissolved so1 VfiXce^clTeffects
?nMntKxwf^yf9t> Internal
the elements being determined.
• , . maibapv interferences - Result when Isotopes of elements 1n a
415 prevl ousswiplecontrl bute to the signals «asureda»n«
eamnio Hcmorv effects can result from sample deposition on
the sampler and skimmer cones, and from
material in the plasma torch and spray chamber. The site
where these effects occur is dependent on the «^eJ®^.and can
be minimized by flushing the system
between samples (Sect. 7.6.3). Thepossllbil«aiytical run
interferences should be recognized within an analytical run
and suitable rinse t1»es should be used to The
rinse ti.es necessary for a part cuUr be
estimated prior to analysis. This may be acmevea oy
aspirating a standard containing ele«ents corresponding to
US uks the upper end of the linear range for a normal
saSpl^analysis period, followed by ^1* re Sl ed
blank at designated intervals. The length of time required
to reduce analyte signals to within a factor of ten
method detection limit, should be noted. Memo^ ,
interferences may also be assessed within an analytical run
bj SuHrrSlnta- of three replicate^rations for data
acquisition. If the integrated signal value:s dirop
consecutively, the analyst should be alerted to the
possibility of a memory effect, and should1®x!JilJ5eni!fY if
analyte concentration in the previous sample to Identify If
this was high. If a memory interference Is suspected, the
sample should be reanalyzed after a long rinse period.
SAFETY
5.1
88
-------
5.2
*«tontiai health hazard and exposure to these compounds should be as
M'aA WtS*3S«" M jwfc7
reference file of material data handling sheets should also be
available to all personnel involved In the chemical analysis.
Analytical olasma sources emit radlofrequency radiation In «M1t1on
to Intense UV radiation. Suitable precautions should be taken to
protect personnel from such hazards.
APPARATUS AND EQUIPMENT
6.1 INDUCTIVELY COUPLED PLASMA - MASS SPECTROMETER
fi 1 l Instrument capable of scanning the mass range 5-250 amu with
i minimum resolution capability of 1 amu peak width at 5%
peak height. Instrument may be fitted with a conventional or
extended dynamic range detection system.
6.1.2 Argon gas supply (high-purity grade, 99.99%).
6 1 3 A variable-speed peristaltic pump is required for solution
delivery to the nebulizer.
s l 4 A mass-flow controller on the nebulizer gas supply is
re£S"ed A water-cooled spray chamber may be of benefit in
reducing some types of interferences (e.g., from polyatomic
oxide species).
6.1.5
Ooerating conditions - Because of the diversity of Instrument
hardware no detailed instrument operating conditions are
Divided! The analyst is advised to follow the recomjended
operating conditions provided by the.;anjJaJtjr®r;n5J^J1?ni
resDonslbility of the analyst to verify
eonfiauration and operating conditions satisfy the analytical
requirements and to maintain quality control data v®ri^J9
instrument performance and analytical results. Instrument
operating conditions which were used to generate P^slon
and recovery data for this method (Sect. 13) are Included In
Table 6.
fi l 6 If an electron multiplier detector 1s being used, PrecJu^®||ji
should be taken, where necessary, to prevent exP
-------
contamination sources '"'J^nl^UhlS thSl^^y
apparatus and general contwlnat on within.the 1IttrM»»_
r^lSnStld fo^raJe il^nt sample handling must be used. Saple
conttmers can introduce ^it1ve J^ ^JtW^r»rs (jMi6jnU
wu&r&srs1i&M;««.crr
centratlons through adsorption processes. All reuseable^laej.^
SeSlgSi lISui£roU9iiyn«S5^0-^5
®B?3® KSS?5" • -
NOTE: Chromic acid must not be used for cleaning glassware.
6.2.1 Glassware - Volumetric flasks, graduated cylinders, funnels
and centrifuge tubes.
6.2.2 Assorted calibrated pipettes.
6-2-3 assslasses-
624 (fluorinated^ eth^l SeToS? eSe^i thj ef» J/JgjfW ene
tetrafluorethylene) screw closure, 125-»L and 250 «l
capacities.
6 3 SAMPLE PR0CESSIN6 EQUIPMENT
•" s^:«s,rsivfl!sv'Ms
high quality disposable pipet tips.
6.3.2 Balance - Analytical, capable of accurately weighing to
0.1 mg.
6.3.3 Hot Plate - (Corning PC100 or equivalent).
6.3.4 Centrifuge - Steel cabinet with guard bowl, electric ti«er
and brake.
6.3.5 Drying Oven - Gravity convection oven with thermostatic
control capable of maintaining 105 C ± 5 C.
PFAGFNTS *nn CONSUMABLE MATERIALS
90
-------
MS high-purity reagents should be usedxhenever Possible^ All
Kids used for this Btthod «ust be of ultra hi9h-pur ty grade.
Suitable acids are available from a number of manufacturers or way
be prepared by sub-boiling distillation. Nitric add is preferred
for ICP-MS in order to minimize polyatomic ion inJeJ!fer?!Jcef: ,,
Several polyatomic ion interferences result when I^[°5 ![{!:
is used (Table 2), however, it should be noted that hydrochloric
«1d is required to «ia1nt»in stability in solutions c0.Ui.ln9
antimony and silver. When hydrochloric acid is used, corrections
for the chloride polyatomic ion Interferences must be applied
data.
7.1.1 Nitric acid, concentrated (sp.gr. 1.41).
7 1 2 Nitric acid (1+1) - Add 500 mL conc. nitric acid to 400 wL of
ASTM type I water and dilute to 1 L.
7.1.3 Nitric acid (1+9) - Add 100 mL conc. nitric acid to 400 tL of
ASTM type I water and dilute to 1 L.
7.1.4 Hydrochloric acid, concentrated (sp.gr. 1.19).
7 1.5 Hydrochloric acid (1+1) - Md 500 .1 conc. hydrochloric Kid
to 400 mL of ASTM type I water and dilute to 1 L.
7.1.6 Hydrochloric acid (1+4) - Add 200 mL conc. hydrochloric acid
to 400 mL of ASTM type I water and dilute to 1 L.
7.1.7 Ammonium hydroxide, concentrated (sp.gr. 0.902).
7.1.8 Tartaric acid (CASRN 87-69-4).
7 2 WATER - For all sample preparation and dilutions, ASTM type I
(ASTM D1193) is required. Suitable water may be prepared by passing
distilled water through a mixed bed of anion and cation exchange
resins.
7.3 STANDARD STOCK SOLUTIONS - May be purchased $
comnercial source or prepared from ultra high-purity grade cnemicais
motalc fQQ 99 - 99.999% pure). All salts should be dried for 1 h
at 105*C, unless otherwise specified. (CAUTION: Many S hiw
are extremely toxic if inhaled or swallowed. Mash hands thoroughly
after handling). Stock solutions should be stored in Teflon
bottles. The following procedures may be used for preparing stan-
dard stock solutions:
NOTE: Some metals, particularly those «•>'<*J""
reauire cleaning prior to being weighed. Jhis may be achieved oy
Dicklina the surface of the metal in acid. An amount in excess of
the desired weight should be pickled repeated!y»f^ed with water,
dried and weighed until the desired weight is achieved.
91
-------
ssrs srSbW:
KX"».".SffiiE -ifS-j.
to 4 2 Cool and add « wL AST* type I wUer. He.t
until the volume 1s reduced to 2 «L. Cool and dilute to
100 ml with ASTM type I water.
7 2 2 Antimony solution, stock 1 mL - 1000 Mg Sb: Dissolve 0.100 g
aStS powder \h 2 mL (1+1) nitric acid and 0.5 mL conc.
hydrochloric acid, heating to effect solution. Cool, *^
a|! _| actw tuna t ustpr 2nd 0.15 Q tjrtiric icld. ?
JSlftlSuT,£Z?vim-it. pr«cip't»te. Cool and dilute
to 100 ml with ASTM type I water.
7 3 3 Arsenic solution, stock 1 mL - 1000 m9 As: Dissolve 0.1320 g
7.3.3 Arsen ^ ^ mixture of 50 mL ASTM type I water and 1¦ "Ljonc.
anmonium hydroxide. Heat gently to d1"olJe;fi5 D??Jte to
acidify the solution with 2 ml conc. nitric acid. Dilute to
100 mL with ASTM type I water.
7 3 < Barium solution, stock 1 «L - 1000 M Ba: Dissolve 0.1437 9
D,fn tn a solution mixture of 10 nL ASTH type I water and
2 al3conc. "trie acid. Heat and stir to ef ec solutlon and
degassing. Dilute to 100 mL with ASTM type I water.
70c Rorvllium solution, stock 1 mL - 1000 jig Be: Dissolve
1 965 a BeSO 4H,0 (DO NOT DRY) 1n 50 «L ASTM Type I water.
M1 il «nc- niVrlc «M. Dilute to 100 .1 with ASTH type
I wstcr*
9
Cool and dilute to 100 mL with ASTM type I water.
7 3 7 Cadmium solution, stock 1 mL - 1000 n Cd: Pickle cadmium
metal in (1+9) nitric acid to an exact weight of 0.100 g.
Dissolve in 5 mL (1+1) nitric acid, heating to effect
solution. Cool and dilute to 100 mL with ASTM type I water.
7.3.8 Chromium solution, stock 1 mL-1000 W Cr: ^«olv*
0 1923 q CrO* 1n a solution mixture of 10 mL ASTM type I
water and lmL conc. nitric acid. Dilute to 100 mL with ASTM
type I water.
7 3 9 Cobalt solution, stock 1 mL - 1000 M Co: Pickle cobalt
metal 1n (1+9) nitric acid to an exact weight of 0.100 g.
Oissolve in 5 mL (1+1) nitric acid, heating to effect
solution. Cool and dilute to 100 mL with ASTM type 1 water.
92
-------
7-3i°
* MW &T. «t.r.
7.3.11 lS°J*Kt «(sMk«f o"l0o"9.
•»& wv-JSAn,
type I water.
7'3'13 HUTw l"w-MM) St'rlM K^°o tffect
silSuoS.^oil iSd dilute to 100 * »Uh AST* type I «ter.
7.3.14 Hanganese *JSknit" 1 c".ild"t^aU"^x"t"illght of
gE^^aa.-w.'KW'-1
water.
7.3.15
Molybdenua solution, stock 1 «L - 1000 M ^Dissolve
o 1500 a MoO* in a solution mixture of 10 mL win yp
Mter and laL cone, imonlun hydroxide., heat'Ing ti»
-------
nII Thallium solution, stock 1 «L • 1000 M9 TV. 01 ssojve
0 1303 9 T1M0, in a solution mixture of 10 ml AST* type J
water and lei cone, nitric acid. Oilute to 100 mL with ASTM
type 1 water.
7 3 22 Thorium solution, stock 1 .L - 1000 « Th: Dissolve 0.23S0 g
Th(N01)4.4H20 (DO HOT DRV) in 20 «L AST* type 1 water.
Dilute to foo «L with AST* type I water.
7 3 M Uranium solution, stock 1 mL - 1000 j*9 l»: Dissolve 0.2110 9
Uo!(NoT)2 6HJ) (DO NOT DRY) in 20 mL ASTM type I water and
diVute £o rto «L with ASTM type I water.
7 3.24 Vanadium solution, stock 1 mL - 1000 pg V: Pickle v.nadi«
¦etal in (1+9) nitric acid to an exact weight of 0.100 g.
Dissolve InlVUHl) nitric jcil.^il,™ JUTS waUr
solution. Cool and dilute to 100 iL with ASTM type I water.
7 3 25 Yttrium solution, stock 1 id. - 1000 pg Y: Oissolve 0.1270 g
Y 0 in 5 ml (1+1) nitric acid, heating to effect solution.
C&l and dilute to 100 .1 with AST* type 1 water.
7 3 26 Zinc solution, stock 1 mL - 1000 pg Zn: Pickle
(l+« n trie acid to an exact weight of 0.100 g. Dissolve in
5 mL (1+1) nitric acid, heating to effect solution. Cool and
dilute to 100 «l with ASTM type I water.
, T.ci chcut stock STANDARD SOLUTIONS - Care Dust be taken In the
a-.
combinations of elements are suggested:
Standard Solution A Standard Solution B
Aluminum Manganese Barium
Antimony Molybdenum Silver
Arsenic Nickel
Beryllium Selenium
Cadmium Thallium
Chromium Thorium
Cobalt Uranium
Copper Vanadium
Lead Zinc
Multielement stock standard solutions A and B(1 »L - 10 eg) may be
prepared by diluting 1 mL of each single element stock in the
94
-------
7.5
7.6
conbination list to 100 * «Uh ASTH type I water containing 1*
(v/v) nitric acid.
sea s^a«Ss3srSr
&S2Sr^&£%f-:
a,a^sa3faj?i."aw »" s»:«.
quality control sample (Sect. 7.8).
INTERNAL STANDAROS STOCK SOLUTION. 1 *- 10° ^ ®f
scandlun, yttriuj, India, terbta. .^ ^~tb1^oc$^n , Tefl0n
S^c1d- ,f^e internal standards are
being added by peristaltic pump (Method B, Sect. *.t)
instrument
«- -».<«> ks'ws sm r
Sect. 9*1), is being used add internal standards.
sallies. The LRB «ist be carried through the^nt^re^ap e
digestion ®2d.Pr5p?ra|l?* S?»Tis being used, add internal
standards IPS?ArtS'AS prepar.?1.n Is co*>lete.
Rinse blank - Consists of 2% (v/v) nitric acid in ASTH type 1
7.6.3
water.
7.7
TUNING SOLUTION - This solution is ^ for instruct tuning £
mass calibration prior to ana^£ • indiu|n an(j -|ea(j stock solutions
?£?. )7)Tn (v/v) Sn1 trie acid' to produce a concentrat i on of
95
-------
100 nqll of each element. Internal standards are not added to this
solution.
7 a ntiAi tty CONTROL SAMPLE (QCS) - The QCS should be obtained from a
7 8 Dilute « .pproprUt. .11,uot of
analytes (concentrations not to exceed 1000 W/L)»jj 1* W )
nitric acid If the direct addition procedure (Method A, Sect. 9.2)
"1Sin?is4d!aS3Internal standards after dilution, «1x and store
In a Teflon bottle.
7.9 LABORATORY FORTIFIED BLANK (LFB) - To *n i^iquot of LRB, add
aliauots from multielement stock standards A and B (Sect. 1
produce a final concentration of 100 w/L for each awlyte. The
LFB must be carried through the entire sample digestion and
preparation scheme. If the direct addlt1°npr^cedure (Method A,
Sect. 9.2) 1s being used, add Internal standards to this solution
after preparation has been completed.
8. sample COLLECTION. PRESTATION AND STQRA3E
8 1 Prior to sample collection, consideration should be 9^en to the
tuna nf riata reauired so that appropriate preservation and
^relt^J «n be tUeJ. F11trat1», add preservation,
etc.. should be performed at the time of sample collection or as
soon thereafter as practically possible.
8 2 Z ^'oV^e
LSv.ri au
acid Immediately following filtration to pH < 2.
a 3 For the determination of total recoverable elements In a^ous
caLiat aeldifv with (1+1) nitric acid at the time of collection to
3T! J inlSlSllJ 3 mL of (1+1) nitric acid per liter of sample is
SfficiLt for iist ambient and drinking water samples). The sample
should not be filtered prior to analysis.
NOTE: Samples that cannot be acid preserved at the time of
collection because of sampling limitations or transport
restrictions should be acidified with nitric acid to pH < 2 upon
receiot in the laboratory. Following acidification, the sample
shoSld biheld for 16 h before withdrawing an aliquot for sample
processing.
8.4 Solid samples usually require no preservation prior to analysis
other than storage at 4°C.
96
-------
Cfl IRMTIOM ftffl CTftHPftPP12AT10N
9.1 CALIBRATION - l""'11
^ES'SrlidjS11,
results of cont nu ^ cal br.tlon checks^ Aner^ ^ ^ ^
endSofC«ch period dicing ^Ich analyses are perfo^. and at
requisite Intervals.
lisisplS-
saMS-»
SKSXV"~££fS ••¦ — <™ •»
mass.
9.1.2 Instrument stability «t fReTta?**
resultl^ relatlve^Undard deviates .f absolute signals
for all analytes of less than 5%.
9.1.3 Prior to initial cj'?;.!j'^^alJsls^The^struniint
software routines (For quanttlUtlv.^inalys^
"!st Is™ M.Jk (Sect 7 6.1) and calibration standards
^^B rS c M reparei at ine or »re concentration
?e$s A«tn1«unof three replicate Integrations are
for>1nstru«ent°calibratlon 3 dlta reporting.
SUff^gS£^?ig3&.
be established.
tntfrnal STANDARDIZATION - Internal standardization must be used 1n
Interferences. VU m^l« ™n£e scans a minimum of three Internal
Tta^rds'iust'be used '.SSdSdST
"sAU. ^^'ss&w^rjsa.10
MS present 1n a'l saipl es, standards and
9.2
97
-------
at identical levels. This nay be achieved by directly adding
an aliauot of the Internal standards to the CAL standard, blank or
samle solutton(Method A, Sect. 9.2). or alternatively by .Ulng
with the solution prior to nebulUatlon using a second channel of
the neristaltic pump and a Mixing coll (Method B, sect.»•*/•
concentration of the internal standard should be
that good precision 1s obtained in the P
used for data correction and to minimize the possibility °'
correction errors If the internal standard Is naturallyj'»
the sample. A concentration of 200 M9/L of each Internal standar
is recommended. Internal standards should bet.
samples and standards in a like »»nner, 80J**1 di1ution effects
resulting from the addition may be disregarded.
9 3 INSTRUMENT PERFORMANCE - Check the performance of the instrument and
verify the calibration using data gathered fro. iinalyses of
calibration blanks, calibration standards and the quality control
sample (QCS).
9 3 1 After the calibration has been established, it must be
initially verified for all analytes by analyzing the QCS
(Sect. 7.8). If measurements exceed ± 10% of the
established QCS value, the analysis should ^terminated, the
source of the problem identified and corrected, the
instrument recalibrated and the calibration reverifled before
continuing analyses.
9 3 2 To verify that the instrument is properly
continuing basis, run the calibration blank and « 1b™tion
standards as surrogate samples after every ten
results of the analyses of the #t^Jrts
whether the calibration remains valid. If the Indicated
concentration of any analyte deviatesfrom the true If
concentration by more than 10%, reanalyze the standard. If
the analyte is again outside the 10% limit, the instrument
must be recalibrated and the previous ten samples reanalyzed.
The instrument responses from the calibration check
u«»d for recalibration purposes. If the sample matrix is
respons 1 ble for the calibration drift it is recommended that
the previous ten samples are reanalyzed in ?£tf
between calibration checks to prevent a similar drift
situation from occurring.
10. QUALITY CONTROL
10 1 Each laboratory using this method is required to operate a formal
quality control (QC) program. The minimum of this
oroaram consist of an initial demonstration of laboratory
capability, and the analysis of laboratory reagent blanks, fortif e
blanks and samples as a continuing check on performance.
98
-------
laboratory is required to wlntain performance records that define
the quality of the data thus generated.
10.2 INITIAL DEMONSTRATION OF PERFORMANCE
10"21 Iharicter*zed1^tru!ient0perfo™anc™!iethod S&tf. IMt.
STltaSJ llSrttSrranges) f* conducted by tkis
method.
10.2.2 Method detection ll.lts (HDL) *"
»n»lytes, using reagent wate ^ estiMted detection
S.5 WSSflS S»
SSs "
the appropriate units. Calculate the MDL
MOL - (t) x (S)
u „ ~ student's t value for a 99% confidence level and
' * " f ntndart d"l.t1on esttwte «1th n-1 degrees
Jf freedom [t - 3.14 for seven replicates].
S « standard deviation of the replicate analyses.
Mm c should be determined every six months or whenever a
significant change in background or instrument response is
expected (e.g., detector change).
10.2.3 Linear calibration range^- Wj^^lVSTllEr
cal"i brat ion range should be established for each analyte by
dotarminina the signal responses from a minimum of three
sisis-f to
avo1dPpotent1al danage to the detector during ^this
SlMry iMTaSJrTs?« change
f"™tr^nt %Spo«e Is expects (e.g.. detector change).
10.3 ASSESSING LABORATORY PERFORMANCE - REAGENT AND FORTIFIED BLANKS
10 3 1 Laboratory reagent blank (LRU) - The laboratory ®"st ana1yze
10.5.x L®D!?r* * .go /Cprt 7 6.2) with each set of samples, lkd
data .4 u«d fo assess contaiination fro. the "Moratory
environment and to ch>r»cteriz^spectCi\^a^rte ill
rhe9er"ta9eStedbUnnkSe«leedsTu"ren.ined HDL, then laboratory
99
-------
or reagent contamination should be suspected.
source of contamination should be corrected end the suples
reanalyzed.
10-3'2 SS5?3
IS??)- 55# SK&
limits (£t. li3.3)/thu analyte1s ^
control, and the source of the problem should be Identified
and resolved before continuing analyses.
10 3 3 Until sufficient LFB data become a
of 20 to 30 analyses), the laboratory JS*JS|5 n5X
laboratory performance against recovery 11 i^ts of 85-115%.
When sufficient internal performance data becomes available,
£«lopcoStlSl 11 "its fro* the percent mean recovery (x) and
the standard deviation (S) of the Kan recovery. These data
are used to establish upper and lower control limits as
follows:
UPPER CONTROL LIMIT - x + 3S
LOWER CONTROL LIMIT - x - 3S
if*ar aarh five to ten new recovery measurements, new control
limits should be calculated using only the most recent twenty
to 30 data points.
4 ASSESSING ANALYTE RECOVERY - LABORATORY FORTIFIED SAMPLE MATRIX
in a i thp laboratory must add a known amount of analyte to a
10'4'1 of the
thMi concentration'should be the same as that 13 ft'
Se fES lUct 10 l") For solid samples, the concentration
added shou 1 dte50 «g / *9 equivalent (100^/Lln the
analysis solution). Over time, sa«ples from all routine
sample sources should be fortified.
io 4 2 Calculate the percent recovery for each analyte,
10-4'2 for:baf4roundPconcentrat1ons measured 1n ^ unfortified
sample, and compare these values to the control imits
established in Sect. 10.3.3 for the analyses of LFBs.
Recovery calculations are not require! if the concentration
of the analyte added is less than 1W of the sample
background concentration. Percent recovery^ "loilated
in units appropriate to the matrix, using the following
equation:
C, - C
R . X 100
100
-------
where, R • percent recovery
C - fortified sample concentration
C* • sample background concentration
s ¦ concentration equivalent of
fortifier added to sample.
10 4 3 If recovery of any analyte falls outside the designated range
and laboratory performance for that analyte 1s shown to JeJn
control (Sect. 10.3), the recovery problem encountered with
the fortified sample 1s judged to be Mtrix not
system related. The result for that analyte in the^
unfortified sample must be labelled "susPect/"atr1Jliat?
Inform the data user that the results are suspect due to
matrix effects.
Mch^thel*^ ThU^fomationmay
be used to detect potential problems caused by mass dependent drift,
errors incurred in adding the Internal standards or increases in the
concentrations of individual internal standards caused by background
"ntrlSUn" fr« the sa*le The absolute «sponseof any on.
internal standard should not deviate more than 60-lZ5% of tne
J?1glMl mwnse In the calibration blank If Aviations neater
than this are observed, use the foilowing test procedure.
10 5 1 Flush the instrument with the rinse blank and monitor the
responses in the calibration blank. If the responses of the
internal standards are now within the limit, take a fresh
aliquot of the sample, dilute by a further factor of two, add
the internal standards and reanalyze.
in q 7 If test fSect. 10.5.1) is not satisfied, or if it is a blank
or calibration standard that is out °[ Risible
analysis, and determine the cause of the drift. Possible
causes of drift may be a partially blocked sampling cone or a
change in the tuning condition of the instrument.
11. PROCEDURE
11.1 SAMPLE PREPARATION - DISSOLVED ELEMENTS
11 1 1 For determination of dissolved elements in drinking water,
ground and surface waters, take a 100 mL al quot of the
filtered acid preserved sample, and add 1 mL
nitric acid. If the direct addition procedure (Method A) Is
being used, add internal standards and mix. The f J™j£e ,
now ready for analysis. Allowance for sample dilution should
be made in the calculations.
101
-------
mote- If a orectpltate 1s formed during acidification,
transport or storage, the sample aliquot must be treated
using the procedCrl in Sect!ll.2.1 prior to analysis.
SAMPLE PREPARATION - TOTAL RECOVERABLE ELEMENTS
oreserved sample containing not "ore than o.z» ij/vj
85'C until the volume has been reduced toapproximately 20
ml ensuring that the sample does not boil. A JPar®J™e
Sd3S5tnthI te^eraturetcontrolbofUthe hot'pfaU such that an
srs fe'ra £ -
8r„,sss«.»w!s ™"»«
STA-aM T.3SMy sl:
HKH3 « #|§feaS5
rvlinder Dilute to volume with ASTM type I water ana «ia
Centrifuge the sample or allow to stand overnight "
Insoluble material. Prior to analys s, pipette20 .L Into a
S0-«L vol metric flask, dilute to volume mth ASTM type I
. j miy if the direct addition procedure (Method A,
water and m x f the d rect » Standards and m x.
t5 liJill is now ready for analysis. Because the stability
of diluted samples cannot be fully cha™^®5l£S'after the
analyses should be performed as soon as possible after the
completed preparation.
11 2.2 For determination of total recoverable elements 1»»lid
camnles (sludae, soils, and sediments), mix the sample
thoroughly to achieve homogeneity and weigh ,
To ol 9 Portion of the sample. Transfer to f »0-«L
ohnTins beaker Add 4 mL (1+1) nitric acid and 10 mL (1+4)
HC1 Cover with a watch glass, and reflux the sample on a
hot * nlate for 30 min. Very slight boiling may occur,
however vigorous boiling must be avoided to prevent the loss
of the HC1-H20 azeotrope. (MOTE: Adjust th® ^
rsf
but no higher than 85°C). Allow the sample to cool, and^
quantitatively transfer to a 100-mL volumetric flask.
Dilute
bU • iwv mi-
102
-------
. 1lim# with ASTM tvDe I water and mix. Centrifuge the
sample or allow to stand overnight to tflS0l?rt?
Material. Prior to analysis, pipette "J1- Into a 5°-«L
volumetric flask and dilute to vo «e with ASTH type water.
If the direct addition procedure (Method A, Sect. is
hoina used add Internal standards and ilx. The sample 1s
noi^ready^for analysis* Because the effects .f various
natrices on the stability of diluted samples cannot be
"£cUr?z«S,.11 analyses should be perfomed as soon as
possible after the completed preparation.
NOTE- Determine the percent solids 1n the sample for use in
calculations and for reporting data on a dry weight basis.
l 3 For every new or unusual matrix, It is highly recommended that a
I.3 ror eve y aiv.i. k. carried out to screen for high element
corral oil Information^ gainedfrom this may be used to prevent
potential damage to the detector during sample analysis and to
for background levels of all elements chosen for use "^nterna!
standards in order to prevent bias in the calculation of the
analytical data.
II.4 Initiate instrument operating oonNsuratlMj. Tune and calibrate the
instrument for the analytes of interest (Sect. 9).
ii c cetshiich instrument software run procedures for quantitative
s For all sanple analyses, a minimum of three replicate
tUtatione are reouired for data acquisition. Discard any
integrations S?c™r4 «n idered to je .ututic.l fliers and use
the average of the integrations for data reporting.
J Sut? bi iSn1tS!2d in tSe sa« scan as is used for the collection
of the data. This information should be used to correct the data
for identified interferences.
11 7 The rinse blank should be used to flush the system betmeen samples.
Iii«l efficient tine to remove traces of the previous sayle or a
mi ni»umof one iinute. Sanples should be aspirated for 30 sec prior
to the collection of data.
11 8 Savvies having concentrations higher than the established linear
dJSmlc range should be diluted Into range and reanalyzed. The
sample should first be analyzed for the trace '
SiBplets')r?fenecessary 'b^the^election of appropriate scanning
:]£!• The sample should then be diluted fZ the deten.in.tion of
103
-------
the remaining elements. Alternatively, the dynamic range may be
adjusted by selecting an alternative Isotope of lower natural
abundance, provided quality control data for that l5°J®p®1{^?^een
established. The dynamic range must not be adjusted by altering
instrument conditions to an uncharacterized state.
12. CALCULATIONS
12 1 Elemental equations recommended for sample data calculations are
listed in Table 5. Sample data should be reported 1n units of hq/1
for aqueous samples or mg/kg dry weight for solid samples. Oo not
report element concentrations below the determined MuL.
12 2 For data values less than ten, two significant figures should be
used for reporting element concentrations. For data values greater
than or equal to ten, three significant figures should be used.
12.3 Reported values should be calibration blank subtracted. For aqueous
samples prepared by total recoverable procedure (Sect. 1J-2-1),
multiply solution concentrations by the dilution factor 1.25. For
solid samples prepared by total recoverable (*®^V *
11 2 21 multiply solution concentrations (jig/L in the analysis
solution) by the dilution factor 0.5. If di1uJj2HS<.!ferS~
made to any samples, the appropriate factor should be applied to the
calculated sample concentrations.
12.4 Data values should be corrected for Instruct drift or saspU
matrix induced interferences by the application of Internal
standardization. Corrections for characterized spectral
interferences should be applied to the data. Chloride interference
corrections should be made on all samples, regardless of the
addition of hydrochloric acid, as the chloride ion Is a common
constituent of environmental samples.
12.5 If an element has more than one monitored isotope, examination of
the concentration calculated for each isotope, or the J5?*0*!® ti
ratios, will provide useful information for the analyst in detecting
a possible spectral Interference. Consideration should therefore be
given to both primary and secondary isotopes In the evaluation of
the element concentration. In some cases, sw?Pdar*.*s°*?jJ®* Bay
less sensitive or more prone to interferences than the primary
recommended isotopes, therefore differences between the results do
not necessarily Indicate a problem with data calculated for the
primary isotopes.
12.6 The QC data obtained during the analyses provide an *n<1jjation
the quality of the sample data and should be provided with the
sample results.
104
-------
3. fBftmw "" *ccultACY
1 srs^'asrs sa.T
determined using the procedure described in Sect. 10.2.2, are nstea
in Table 7.
13.2 Data obtained fro. single lavatory testing of the «th* are
^ -filler! ground water^and^aste effluent. Samples^
t?e mlM ^favlrage'of the
reollcates used for determining the sa*>le background concentration
repncaies uw. iv f,1Pther oalrs of duplicates were fortified at
different concentration levels.' For each method el««nt the sample
background concentration, mean percent J
deviation of the percent recovery and the relative percent
difference between the duplicate fortified samples are listed
Table 8.
13.3 Data obtained ^single
lM^RIver Sediment, EPA Hazardous Soil and EPA Electroplating
A, bSJrXi"
duplicate fortified samples were determined as for Sect. 13.2.
14. REFERENCES
1. A. L. Gray and A. R. Date, Analyst IflS 1033 (1983).
2. R. S. Houk et al. Anal Chem. 51 2283 (1980).
3. R. S. Houk, Anal. Chen. 5fi 97A (1986).
4. J. J. Thompson and R. S. Houk, Appl. Spec. 41 801 (1987).
"OSHA Safety and Health Standards, General Industry," (29 CFR 191°),
oSKJatloSl Safe™ and Health Administration, OSHA 2206, revised
January 1976.
"Prooosed OSHA Safety and Health Standards, Lab;rJ^jes'"
Occupational Safety and Health Administration, Federal
Register, July 24, 1986.
7. Code of Federal Regulations 40, Ch. 1, Pt. 136 Appendix B.
5.
6.
105
-------
TABLE 1: ESTIMATED INSTRUMENT DETECTION LIMITS
ELEMENT
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Lead
Manganese
Molybdenum
Nickel
Selenium
Silver
Thallium
Thorium
Uranium
Vanadium
Zinc
RECOMMENDED
ESTIMATED IDL
ANALYTICAL MASS
(M9/L)
27
0.05
121
0.08
75
0.9
137
0.5
9
0.1
111
0.1
52
0.07
59
0.03
63
0.03
206.207,208
0.08
55
0.1
98
0.1
60
0.2
82
5
107
0.05
205
0.09
232
0.03
238
0.02
51
0.02
66
0.2
Instrument detection limits (3a) estimated from seven replicate
integrations of the blank (1% v/v nitric acid) of
the instrument with three replicate integrations of a multi-element
standard.
106
-------
TABLE 2: COMMON MOLECULAR ION INTERFERENCES IN ICP-NS
BACKGROUND MOLECULAR IONS
Molecular Ion
NH*
OH*
0H2*
r *
CN*
CO4
n2*
n2h*
NO*
NOH*
o2h*
"ArH*
MArH+
40ArH*
C02*
C02H+
ArC*,ArO+
ArN*
ArNH*
ArO*
ArOH*
40Ar36Ar+
40ArMAr*
40Ar2*
Mass
15
17
18
24
26
28
28
29
30
31
32
33
37
39
41
44
45
52
54
55
56
57
76
78
80
Eleaent Interference*
Sc
Cr
Cr
Mn
Se
Se
Se
method elements or internal standards affected by the molecular ions.
107
-------
TABLE 2 (Continued).
MATRIX MOLECULAR IONS
mORICE
Molecular Ion
35C10H*
I7C10*
37C10H*
Arfcr
Ar CI*
SULPHATE
Molecular Ion
KSOH*
^SO*
*SOH*
S02', S2+
Ar3V
Ar S*
PHOSPHATE
Molecular Ion
PO*
POH+
P02+
ArP*
GROUP I, II HETALS
Molecular Ion
ArNa*
ArK+
ArCa*
MATRIX OXIDES*
Molecular Ion
T10
ZrO
MoO
Mass
51
52
53
54
75
77
Mass
48
49
50
51
64
72
74
Mass
47
48
63
71
Mass
63
79
80
Masses
62-66
106-112
108-116
Element Interference
V
Cr
Cr
Cr
As
Se
Eleaent Interference
V,Cr
V
Zn
Eleaent Interference
Cu
El
nt Interference
Cu
Eleaent Interference
N1,Cu,Zn
Ag.Cd
Cd
S&SS® fas sxwjest.
monitored as a method analyte.
108
-------
TABLE 3: INTERNAL STANDARDS AND LINITATIONS OF USE
Internal Standard
Hass
Possible Limitation
^Lithium
Scandium
Yttrium
Rhodium
Indium
Terbium
Holmium
Lutetium
Bismuth
6
45
89
103
11S
159
165
175
209
a
polyatomic ion interference
».b
isobaric interference by Sn
a
a Hay be present 1n environmental samples. . f Yn* no5 amu\
b In some instruments Yttrium may form measurabl e a^unts of YO in the use
and YOH* (106 amu). If this is the case, care should be taken in the use
of the cadmium elemental correction equation.
Internal standards reco«ended for use with thts Kthod are shom ln bold
face. Preparation procedures for these are included in section 7.3.
109
-------
TABLE 4: RECOMMENDED ANALYTICAL ISOTOPES AND ADDITIONAL
MASSES WHICH MUST BE MONITORED
Isotope
2Z
1*1,123
Z5
135,121
a
106,108,111.11*
52,53
52
61,65
2S5,207,2QS
55
95.97.2S
77,Si
127,109
203,205
232
238
51
55,67.68
83
99
105
118
Element of Interest
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromi um
Cobalt
Copper
Lead
Manganese
Molybdenum
Nickel
Selenium
Silver
Thallium
Thori um
Uranium
Vanadium
Zinc
Krypton
Ruthenium
Palladium
Tin
NOTE:
Isotopes recoranended for analytical determination are underlined.
110
-------
TABLE 5: RECOMMENDED ELEMENTAL EQUATIONS FOR DATA CALCULATIONS
Elenent
Elemental Equation
A1
(1.000)(27C)
Sb
(1.000)(121C)
As
(i.oooh^cms.izth^cho.sism^c)]
Ba
(1.000)("7C)
Be
(1.000)(9C)
Cd
(1.000)(111C)-(1.073)[(1c8C)-(0.712) (1#6C)1
Cr
(1.000)(52C)
Co
(1.000)(59C)
Cu
(1.000) (aC)
Pb
(1.000) (206C)+(1.000) (207C)+(1.000) (**0
Mn
(1.000) (55C)
Mo
(1.000)(98C)-(0.146)(99C)
N1
(l.OOOM^C)
Se
(l.ooou^c)
Ag
(l.OOO)(107C)
T1
(l.OOOJ^C)
Th
(l.OOOM^C)
U
(l.OOOM^C)
V
(1.000)(51C)-(3.127)[(53C)-(0.113)(52C)]
Zn
(l.OOOU^C)
Note
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Cont.
Ill
-------
TABLE 5 (Continued)
INTERNAL STANDARDS
Element
Elemental Equation
B1
(l.OOOH20^)
In
(1.000)(mC)-(0.016)(mC)
Sc
(1.000)(45C)
Tb
(1.000)(159C)
Y
(1.000)(WC)
Note
(8)
C
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
- calibration blank 1 th'adjustwit'for
" SSTSS H/7f rtJio «y be detained fro. the reagent
. correction for HoO Interference An ^^^"^resent.
elemental conrectlon should be «de^tf pjM>o f ^
" ^i^,fr\hr«»dn Z7» est,..ted fro. the
allowance1 for isotopic variability of lead Isotopes.
- isobar 1c ele^nt.l "^XjpUnas'in Wurlty. Seleniu.
- some argon supplies containkyp btr>ctl0n.
is corrected for KrtZ jy Mc*g™ adjustment for
- ^5eC|iSn5t/S3C«;iod«; frJthe reagent
- isobaric elemental correction for tin.
112
-------
TABLE 6: INSTRUMENT OPERATING CONDITIONS
FOR PRECISION AND RECOVERY DATA
Instrument
Plasma forward power
Coolant flow rate
Auxiliary flow rate
Nebulizer flow rate
Solution uptake rate
Spray chamber temperature
VG PlasmaQuad Type I
1.35 kW
13.5 L/min
0.6 L/min
0.78 L/min
0.6 mL/min
15°C
Data Acquisition
Detector mode
Replicate integrations
Mass range
Dwell time
Number of MCA channels
Number of scan sweeps
Total acquisition time
Pulse counting
3
8 - 240 amu
320 ms
2048
85
3 minutes per sample
113
-------
TABLE 7: TOTAL RECOVERABLE METHOD DETECTION LIMITS
ELEMENT
RECOMMENDED
ANALYTICAL MASS
HDL
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Lead
Manganese
Molybdenum
Nickel
Selenium
Silver
Thallium
Thorium
Uranium
Vanadium
Zinc
27
121
75
137
9
111
52
59
63
206,207,208
55
98
60
82
107
205
232
238
51
66
AQUEOUS
M9/L
1.0
0.4
1.4
0.8
0.3
0.5
0.9
0.09
0.5
0.6
0.1
0.3
0.5
7.9
0.1
0.3
0.1
0.1
2.5
1.8
SOLIDS
¦9/*9
0.4
0.2
0.6
0.4
0.1
0.2
0.4
0.04
0.2
0.3
0.05
0.1
0.2
3.2
0.05
0.1
0.05
0.05
1.0
0.7
•susts'sns!si& »s""
114
-------
TABLE 8 : PRECISION ANO RECOVERY DATA IN AQUEOUS MATRICES
pPTMKTNfi WATER
Sample Low Average
Element Concn. Spike Recovery
115.8
99.1
99.7
94.8
113.5
97.0
111.0
94.*
101.8
97.8
96.9
99.4
100.2
99.0
100.7
97.5
109.0
110.7
101.4
103.4
S(R) RPD
High Average
Spike Recovery S(R) RPD
A1
Sb
As
Ba
Be
Cd
Cr
Co
Cu
Pb
Mn
Ho
Ni
Se
Ag
T1
Th
U
V
Zn
5.9
0.7
0.8
3.9
0.4
2.8
3.5
0.4
8.8
2.0
1.8
1.6
5.7
1.8
1.5
0.4
0.7
1.4
0.1
3.3
0.4
2.0
2.2
5.8
0.9
8.3
9.0
1.1
17.4
2.8
4.7
3.4
13.5
5.3
4.2
1.0
1.8
3.5
0.4
7.7
200
102.7
1.6
1.1
100
100.8
0.7
2.0
200
102.5
1.1
2.9
200
95.6
0.8
1.7
100
111.0
0.7
1.8
100
101.5
0.4
1.0
100
99.5
0.1
0.2
100
93.6
0.5
1.4
100
91.6
0.3
0.3
100
99.0
0.8
2.2
100
95.8
0.6
1.8
100
98.6
0.4
1.0
100
95.2
0.5
1.3
200
93.5
3.5
10.7
200
99.0
0.4
1.0
100
98.5
1.7
4.9
100
106.0
1.4
3.8
100
107.8
0.7
1.9
200
97.5
0.7
2.1
200
96.4
0.5
1.0
35' Rem?;' pereen^differenc^betwee^dupllcate spike delegations.
< Sampl e concentrat i on below established method detection limit.
115
-------
TABLE 8 = PRECISION AMD RECOVERY OATA IN AQUEOUS MATRICES (Cont)
MfLU wwa
Sample
Element Concn.
A1
Sb
As
Ba
Be
Cd
Cr
Co
Cu
Pb
Mn
Mo
Ni
Se
Ag
T1
Th
U
V
Zn
low
Spike
34.3 B
50
0.46 8
10
<1.4 1
50
106 I
50
<0.3 1
10
1.6 I
10
<0.9 1
10
2.4 9
I 1°
37.4 S
10
3.5
10
2770
1°
2.1
1 1°
11.4 |
1 10
<7.9
1 50
<0.1
1 50
<0.3
1 io
<0.1
1 io
1.8
1 10
<2.5
1 so
554
1 50
Average
Recovery
R 1%)
100.1
98.4
110.0
95.4
104.5
88.6
111.0
100.6
104.3
95.2
*
103.8
116.5
127.3
99.2
93.9
103.0
106.0
105.3
*
S(R)
RPD
3.9
0.8
0.9
1.9
6.4
16.4
3.9
3.3
0.4
1.0
1.7
3.8
0.0
0.0
1.0
1.6
5.1
1.5
2.5
1.5
*
1.8
1.1
1.6
6.3
6.5
8.4
18.7
0.4
1.0
0.1
0.0
0.7
1.9
1.1
1.6
0.8
2.1
*
1.2
High
Spike
Average
Recovery
S(R) RPD
200
102.6
100
102.5
200
101.3
200
104.9
100
101.4
100
98.6
100
103.5
100
104.1
100
100.6
100
99.5
100
*
100
102.9
100
99.6
200
101.3
200
101.5
100
100.4
100
104.5
100
109.7
200
105.8
200
102.1
1.1
0.7
0.2
1.0
1.2
0.6
0.4
0.4
0.8
1.4
*
0.7
0.3
0.2
1.4
1.8
1.8
2.5
0.2
5.5
1.3
1.9
0.5
1.6
3.3
1.6
1.0
0.9
1.5
3.9
0.7
1.9
0.0
0.5
3.9
5.0
4.8
6.3
0.5
3.2
S(R) Standard spike determinations.
RPD Relative percent dlpublished method detection limit.
SS^^^cr;tra?nr
-------
TABLE 8 : PRECISION AND RECOVERY DATA IN AQUEOUS MATRICES (Cont).
POND WATER
Sample
Element Concn.
Low Average
Spike Recovery
S(R) RPO
High
Spike
/ iin /I \
Average
Recovery
r m
S(R) RPO
RPO Relative percent difference between duplicate spike determinations.
< Sample concentrat1on below established method detect on 1.11.
* Spike concentration <10% of sample background concentration.
117
-------
TABLE 8 : PRECISION AW RECOVERY DATA IM AQUEOUS RATRICES (Cont).
jpfitmemt PRIMARY EfFUJEHT-
Sample Low Average
Element Concn. Spike Rec°very
fl'V" iw/H—BJSl-
S(R) RPO
A1
1150
Sb
1.5
As
<1.4
Ba
202
Be
<0.3
Cd
9.2
Cr
128
Co
13.4
Cu
171
Pb
17.8
Mn
199
Mo
136
HI
84.0
Se
<7.9
Ag
10.9
T1
<0.3
Th
0.11
U
0.71
V
<2.5
Zn
163
50
10
50
50
10
10
10
10
10
10
10
10
10
50
50
10
10
10
50
50
*
*
3.5
95.7
0.4
0.9
104.2
4.5
12.3
79.2
9.9
2.5
110.5
1.8
4.5
101.2
1.3
0.0
*
*
1.5
95.1
2.7
2.2
*
*
2.4
95.7
3.8
1.1
*
*
1.5
*
*
1.4
88.4
16.3
4.1
112.0
10.9
27.5
97.1
0.7
1.5
97.5
0.4
1.0
15.4
1.8
30.3
109.4
1.8
4.3
90.9
0.9
0.6
85.8
3.3
0.5
High
Spike
l uall.)
Average
Recovery
R l%\
200
100.0
100
104.5
200
101.5
200
108.6
100
106.4
100
102.3
100
102.1
100
99.1
100
105.2
100
102.7
100
103.4
100
105.7
1 100
98.0
200
108.8
H 200
102.6
100
102.0
100
29.3
100
109.3
200
99.4
200
102.0
S(R)
RPO
13.8
1.5
0.7
1.9
0.7
2.0
4.6
5.5
0.4
0.9
0.4
0.9
1.7
0.4
1.1
2.7
7.1
0.7
1.1
2.5
2.1
0.7
2.4
2.1
0.9
0.0
3.0
7.8
1.4
3.7
0.0
0.0
0.8
8.2
0.7
1.8
2.1
6.0
1.5
1.9
S(R) Standard dcvlatP®!!"nier^eeneduplicate spike determinations.
RPO Relative esUblishedmethod detection limit.
* Spike
118
-------
TABLE 8 : PRECISION AND RECOVERY DATA IN AQUEOUS MATRICES (Cont).
fUMISTRIAL EFFLUENT
Sample Low Average
Element Concn. Spike Recovery
fug/1) (ua/i)
S(R) RPD
High Average
Spike Recovery
R (%)
S(R) RPO
A1
Sb
As
Ba
Be
Cd
Cr
Co
Cu
Pb
Mn
Ho
N1
Se
Ag
T1
Th
U
V
Zn
44.7
2990
<1.4
100
<0.3
10.1
171
1.3
101
294
154
1370
17.3
15.0
<0.1
<0.3
0.29
0.17
<2.5
43.4
50
10
50
50
10
10
10
10
10
10
10
10
10
50
50
10
10
10
50
50
98.8
*
75.1
96.7
103.5
106.5
*
90.5
*
*
*
*
107.4
129.5
91.8
90.5
109.6
104.8
74.9
85.0
8.7
*
1.8
5.5
1.8
4.4
*
3.2
*
*
7.4
9.3
0.6
1.8
1.2
2.5
0.1
4.0
5.7
0.3
6.7
3.4
4.8
2.4
0.0
8.7
0.9
2.6
2.8
1.4
5.0
15.1
1.7
5.5
2.7
6.6
0.3
0.6
200
100
200
200
100
100
100
100
100
100
100
100
100
200
200
100
100
100
200
200
90.4
*
75.0
102.9
100.0
97.4
127.7
90.5
92.5
108.4
103.6
*
88.2
118.3
87.0
98.3
108.7
109.3
72.0
97.6
2.1
*
0.0
1.1
0.0
1.1
2.4
0.4
2.0
2.1
3.7
*
0.7
1.9
4.9
1.0
0.0
0.4
0.0
1.0
2.2
0.0
0.0
0.7
0.0
2.8
1.7
1.3
1.6
0.0
1.6
0.7
1.0
3.6
16.1
2.8
0.0
0.9
0.0
0.4
S(R) Standard deviation of percent recovery.
RPD Relative percent difference between duplicate spike determinations.
< Sample concentration below established method detection limit.
* Spike concentration <10% of sample background concentration.
119
-------
TABLE 9 : PRECISION NO RECOVERY DATA I* SOLID MATRICES
fff u.7»PD0U
-------
TABLE 9 : PRECISION AMD RECOVERY DATA IN SOLID MATRICES (Cont).
m IMS RIVER SEDIMENT
Sample Low+ Average
Element Concn. Spike Recovery
finq/kal(me/kg) R i%)
High+ Average
S(R) RPD Spike Recovery S(R) RPD
(mo/kg) B_iX)
A1
5060
20
Sb
21.8
20
As
67.2
20
Ba
54.4
20
Be
0.59
20
Cd
8.3
20
Cr
29100
20
Co
7.9
20
Cu
112
20
Pb
742
20
Mn
717
20
Mo
17.1
20
Ni
41.8
20
Se
<3.2
20
Ag
1.8
20
T1
1.2
20
Th
0.90
20
U
0.79
20
V
21.8
20
Zn
1780
20
73.9
104.3
105.6
88.8
92.9
*
97.6
121.0
*
*
89.8
103.7
108.3
94.8
91.2
91.3
95.6
91.8
*
6.5
13.0
4.9
0.2
0.4
*
1.3
9.1
* *
*
8.1
6.5
14.3
1.6
1.3
0.9
1.8
4.6
9.3
7.6
2.8
0.5
0.0
2.6
1.5
12.0
4.8
37.4
4.3
3.6
2.6
5.0
5.7
100
*
*
-
100
81.2
1.5
3.9
100
107.3
2.1
2.9
100
98.6
2.2
3.9
100
87.9
0.1
0.2
100
95.7
1.4
3.9
100
*
*
-
100
103.1
0.0
0.0
100
105.2
2.2
1.8
100
-
-
-
100
-
-
-
100
98.4
0.7
0.9
100
102.2
0.8
0.0
100
93.9
5.0
15.1
100
96.2
0.7
1.9
100
94.4
0.4
1.3
100
92.3
0.9
2.8
100
98.5
1.2
3.5
100
100.7
0.6
0.8
100
*
*
-
S(R) Standard deviation of percent recovery.
RPD Relative percent difference between duplicate spike determinations.
< Sample concentration below established method detection limit.
* Spike concentration <10% of sample background concentration.
Not determined.
+ Equivalent.
121
-------
TABLE 9 : PRECISION AND RECOVERY OATA IN SOLID NATRICES (Cont).
fi FCTRoriftiirw n#286
Sample Low+ Average
Element Concn. Spike Recovery S(R) RPO
A1
5110
Sb
8.4
As
41.8
Ba
27.3
Be
0.25
Cd
112
Cr
7980
Co
4.1
Cu
740
Pb
1480
Mn
295
Ho
13.3
Ni
450
Se
3.5
Ag
5.9
Tl
1.9
Th
3.6
U
2.4
V
21.1
Zn
13300
1.2
High+ Average
Spike Recovery S(R) RPD
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
*
*
-
61.0
0.2
0.9
94.2
0.8
1.5
0
1.5
10.0
93.4
0.3
0.9
88.5
0.8
0.5
*
*
-
88.7
1.5
4.6
61.7
20.4
5.4
*
*
—
89.2
0.4
1.0
83.0
10.0
4.5
91.0
6.0
18.0
85.1
0.4
1.1
98.9
0.9
2.4
97.4
0.7
2.0
109.6
0.7
1.8
97.4
1.1
2.5
*
*
-
S(R) Standard devUtl°" ^.^""betweerdiplicate spike determinations.
RPO Relative percentesUbiiShed nethod detection 11*11.
Spike'concentration <10% of sample background concentration.
Not determined.
+ Equivalent.
<
*
122
------- |