., u Je*-. n«u««i Publication 9240. 1-25
United States
Environmental Protection Solid Waste and
Agency Emergency Response December 1994
Supertund _ ___
SUPERFUND ANALYTICAL
METHODS FOR LOW
CONCENTRATION WATER FOR
INORGANICS ANALYSIS
REPRODUCED BY
U.S. DEPARTMENT OF COMMERCE
NATIONAL TECHNICAL
INFORMATION SERVICE
SPRINGFIELD, VA 22161
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9240.1-25
PB95-963517
EPA540/R-94/092
SUPERFUND ANALTTICAL METHODS
FOR
LOW CONCENTRATION WATER FOR INORGANICS ANALYSIS
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EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
Page
SECTION I: CONTRACT REPORTS/DELIVERABLES DISTRIBUTION B-l
SECTION II: REPORT DESCRIPTIONS AND ORDER OF DATA
DELIVERABLES B-4
SECTION III: FORM INSTRUCTION GUIDE B-14
SECTION IV: DATA REPORTING FORMS B-45
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SECTION I - CONTRACT REPORTS/DELIVERABLES DISTRIBUTION
' <•« '
The following table reiterates Che Contract reporting and deliverables requirements
specified in the Contract Schedule and specifies Che distribution that is required
for each deliverable. NOTE: Specific recipient names and addresses are subject to
change during the term of the contract. The Sample Management Office (SMO) will
notify the Contractor in writing of such changes when they occur.
1
Item
*****A. Standard
Operating
Procedures
B. Sample Traffic
Reports
**C. Sample Data
Package
D. Data in Computer
Readable Format
****£. Complete SDG
File
*F. Quarterly/Annual
Verification
of Instrument
Parameters
*G. ICP/MS
Diskettes/Tapes
*****H. Quality
Assurance
Plan
| No.
| Copies
3
1
2
1
1
2
Lot
3
Delivery
Schedule
60 days after
contract award,
and as required
in Exhibit E
3 days after
receipt of last
sample in Sample
Delivery Group
(SDG)***
14 days after
receipt of last
sample in SDG
14 days after
receipt of last
sample in SDG
14 days after
receipt of last
sample in SDG**
Quarterly:
15th day of
January , April
July , October
Retain for 365
days after
submission; or
submit them
within 7 days
of written
request by SMO
or EMSL/LV
60 days after
contract award,
and as required
in Exhibit E
| Dis
(1)
X
X
X
X
A.
A.
tributi
(2)
X
X
> direc
> direc
on
(3)
X
X
X
ted
:ed
1 1
(4)
X
B-l
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Distribution:
(1) Sample Management Office (SMO)
(2) Region-Client
(3) Environmental Monitoring Systems Laboratory (EMSL)
(4) National Enforcement Investigations Center (NEIC)
* Also required in each Sample Data Package.
** Concurrent deliveiry of these items to all recipients is required.
*** Sample Delivery Groi,' '~OG) is a group of samples within a Case,
received over a period of 7 days or less and not exceeding 20
samples. Data for all samples in the SDG are due concurrently..
**** Complete SDG File will contain the sample data package plus all
of the original documents described in Exhibit B under "Complete
SDG File." The Complete SDG File must be delivered concurrently
with the Sample Data Package.
*****See Exhibit E for a more detailed description.
NOTE: As specified in the Contract Schedule, unless otherwise
instructed by SMO, the Contractor shall dispose of unused sample volume
and used sample bottles/containers no earlier than sixty (60) days
following submission of analytical data. Sample disposal and disposal
of unused sample bottles/containers is the responsibility of the
Contractor and should be done in accordance with all applicable laws and
regulations governing the disposal of such material.
Distribution Addresses:
(1) USEPA Contract Laboratory Program (CLP)
Sample Management Office (SMO)
P. 0. Box 818
Alexandria, VA 22313
For overnight delivery service, use street address:
300 N. Lee Street, 2nd Floor
Alexandria, VA 22314
(2) USEPA REGIONS: The CLP Sample Management Office will provide the
Contractor with the list of addressees for the ten EPA Regions. SMO
will provide the Contractor with updated Regional address/name lists as
necessary throughout the period of the contract and identify other
client recipients on a case-by-case basis.
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(3) USEFA Environmental Monitoring Systems Laboratory (EHSL)
944 E. Harmon Avenue
Las Vegas, NV 89109
(4) USEPA National Enforcement Investigations Center (NEIC)
Attn: CLP Audit Program
Denver Federal Center Bldg. 53
P.O. Box 25227
Denver, CO 80225
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SECTION II
REPORT DESCRIPTIONS AND ORDER OF DATA DELIVERABLES
The Contractor shall provide reports and other deliverables as
specified in the Contract Performance/Delivery Schedule. The required
content and form of each deliverable is described in this Exhibit.
All reports and documentation shall be:
o Legible,
o Clearly labeled and completed in accordance with instructions in this
Exhibit,
o Arranged in the order specified in this Section,
o Paginated in ascending order, and
o Single-sided.
If submitted documentation does not conform to the above criteria, the
Contractor shall be required to resubmit such documentation with
deficiency(ies) corrected, at no additional cost.
Whenever the Contractor is required to submit or resubmit data as a
result of an on-site laboratory evaluation, a CCS assessment, or through a
SMO action or a Regional data reviewer's request, the data shall be clearly
marked as Additional Data and shall be sent to all three contractual data
recipients (SMO, EMSL/LV, and the Client Region). A cover letter shall be
included which describes which data are being delivered, to which Case(s) the
data pertain, and who requested the data.
Whenever the Contractor is required or requested to respond to Contract
Compliance Screening (CCS) review by SMO, the laboratory response shall be
sent to all three contractual data recipients (SMO, EMSL/LV, and Region). In
all three instances the response shall be accompanied by a color-coded Cover
Sheet (Laboratory Response To Results of Contract Compliance Screening) which
shall be provided in generic format by SMO.
Section IV of this Exhibit contains the required Inorganic Analysis
Data Reporting Forms in specified formats; Section III of this Exhibit
contains instructions to the Contractor for completing all data reporting
forms to provide SMO with all required data. Data elements and field
descriptions for reporting data in computer - readable format are contained in
Exhibit H.
Descriptions of the requirements for each deliverable item cited in the
Contract Performance/Delivery Schedule (see Contract Schedule, Section F) are
specified in parts A-F of this Section. Items submitted concurrently shall
be arranged in the order listed. Additionally, the components of each
deliverable item shall be arranged in the order presented herein when the
item is submitted.
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A. Standard Operating Procedures (SOPs) and Quality Assurance Plan (OAT)
Submit updated SOPs and QAP according to the instructions in Exhibit E.
B. Sample Traffic Reports
The original Sample Traffic Report page marked "Lab Copy for Return to
SMO" with laboratory receipt information and original Contractor
signature, shall be submitted for each sample in the Sample Delivery
Group (SDG) .
Traffic Reports (TRs) shall be submitted in SDG sets (i.e., TRs for all
samples in an SDG shall be clipped together) , with an SDG Cover Sheet
attached.
The SDG Cover Sheet shall contain the following items:
o Laboratory name
o Contract number
o Sample Analysis Price - full sample price from contract.
o Case Number
o List of EPA sample numbers of all samples in the SDG, identifying the
first and last samples received, and their dates of receipt at the
laboratory .
Note: When more than one sample is received in the first or last SDG
shipment, the "first" sample received is the lowest sample number
(considering both alpha and numeric designations); the "last* sample
received is the highest sample number (considering both alpha and
numeric designations) .
Each Traffic Report shall be clearly marked with the SDG number, which
is the sample number of the first sample in the SDG (as described in the
following paragraph) . This information shall be entered below the Lab
Receipt Date on the TR. In addition, the TR for the last sample
received in the SDG shall be clearly marked "SDG - FINAL SAMPLE."
The EPA sample number of the first sample recp'-'^d in the SDG is the SDG
number. EPA field sample numbers are six digits in length. If the
Contractor receives a sample number of any other length, contact SMO
immediately. When several samples are received together in the first
SDG shipment, the SDG number shall be the lowest sample number
(considering both alpha and numeric designations) in the first group of
samples received under the SDG. (The SDG number is also reported on all
data reporting forms. See Section III, Form Instruction Guide.)
If samples are received at the laboratory with multi-sample Traffic
Reports (TRs) , all the samples on one multi-sample TR may not
necessarily be in the same SDG. In this instance, the laboratory shall
make the appropriate number of photocopies of the TR, and submit one
copy with each SDG^cevfer sheet.. 4 . .
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C. ??BTPVs Data
The sample data package shall include data for analysis of all samples
in one Sample Delivery Group (SDG), including but not limited to
analytical samples, field samples, reanalyses, blanks, spikes,
duplicates, laboratory control samples, and FE samples.
The sample data package shall be complete before submission, shall be
consecutively paginated and shall include the following:
*
1. Cover Page for the LC-Inorganic Analyses Data Package, (COVER PAGE —
LC-Inorganic Analyses Data Package), including: laboratory name;
laboratory code; contract number; Case No.; Sample Delivery Group
(SDG) No.; SAS Number (if appropriate); EPA sample numbers in
alphanumeric order, shoving EPA sample numbers cross-referenced with
laboratory ID numbers; comments, describing in detail any problems
encountered in processing the samples in the data package; and,
completion of the statement on use of ICP background and
interelement corrections for the samples.
The Cover Page shall contain the following statement, vffrPflCiP'- "I
certify that this data package is in compliance with the terms and
conditions of the contract, both technically and for completeness,
for other than the conditions detailed above. Release of the data
contained in this hardcopy data package and in the computer-readable
data submitted on diskette has been authorized by the Laboratory
Manager or the Manager's designee, as verified by the following
signature.* This statement shall be followed by the signature of the
Laboratory Manager or the Manager's designee with a typed line below
it containing the signer's name and title, and the date of
signature.
In addition, on a separate piece of paper, the Contractor shall
include any problems encountered, both technical and administrative,
the corrective action taken and resolution.
The Contractor shall retain a copy of the Sample Data Package for
365 days after final acceptance of data. After this time, the
Contractor may dispose of the package.
2. Sample Data
Sample data shall be submitted with the Low Concentration Inorganic
Analysis Data Reporting Forms for all samples in the SDG, including
the PES, arranged in increasing alphanumeric EPA Sample Number
order, followed by the QC analyses data, and Verification of
Instrument Parameters forms, raw data, and copies of the preparation
logs.
a. Results -- Low Concentration Inorganics Analysis Data Sheet
[FORM I - LCIN]
Tabulated analytical results (identification and quantitation)
of the* specified analytes (Exhibit C). The validation and
B-6 10/91
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release of these results is authorized by a specific, signed
statement on the Cover Page. If the Laboratory Manager cannot
verify all data reported for each sample, he/she shall provide
a detailed description of the problems associated with the
sample(s) on the Cover Page.
The quantitative values shall be reported in units of
micrograms per liter (ug/L) for all samples. No other units
are acceptable. Analytical results shall be reported to two
significant figures if the result value is less than 10; to
three significant figures if the value is greater than or equal
to 10.
b. tjXut-lity Control Data
1) Initial and Continuing Calibration Verification [FORM II-
LCIN)
2) CRDL Standards [FORM III-LCIN]
3) Linear Range Standards [FORM IV-LCIN]
4) Blanks [FORM V-LCIN]
5) ICP and ICP/MS Interference Check Sample [FORM VI-LCIN]
6) Spike Sample Recovery [FORM VII-LCIN]
7) Duplicates [FORM VIII-LCIN]
8) Laboratory Control Sample [FORM IX-LCIN]
9) Serial Dilution [FORM X-LCIN]
10) Standard Addition Results [FORM XI-LCIN]
11) Instrument Detection Limits [FORM XII-LCIN]
12) Interelement Correction Factors [FORM XIII-LCIN]
13) ICP/MS Tuning and Response Faccor Criteria [FORM XIV-LCIN]
14) ICP/MS Internal Standards Summary [Form XV-LCIN]
15) Analysis Run Log (A) [FORM XVI-LCIN]
16) Analysis Run Log (B) [FORM XVII-LCIN]
17) Standard Solutions Sources [FORM XVIII-LCIN]
18) Sample Log-In Sheet [FORM DC-1]
19) Document Inventory Sheet [FORM DC-2]
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c. Raw Data
For each reported value, the Contractor shall include in the
data package all raw data from the instrument used to obtain
that value and the QA/QC values reported (except for raw data
for quarterly and annual verifications of instrument
parameters). Raw data shall contain all instrument readouts
used for the sample results, including those readouts that may
fall below the IDL. All instruments shall provide a legible
hard copy of the direct, real-time instrument readout (i.e.,
stripcharts, printer tapes, etc.). A photocopy or other
accurate facsimile of the direct sequential instrument readout
shall be included.
The order of raw data in the data package shall be: ICF,
ICF/MS, HYICP, Flame AA, Furnace AA, Mercury, Cyanide,
Fluoride, and N02/N03-N. All raw data shall include
intensities or concentration for ICP, ICP/MS, HYICP, absorbance
or concentration for AA, spec tropho tome trie measurements, and
millivolts for potentiometric measurements.
Raw data shall be labeled with EPA Sample Number and
appropriate codes, specified in Table 1 Exhibit B, to
unequivocally identify:
1) Calibration standards, including source and
preparation date.
2) Initial and continuing calibration blanks and preparation
blanks.
3) Initial and continuing calibration verification standards,
interference check samples, CRDL standards, linear range
standards, tuning standards, memory test standards and
serial dilution samples.
4) Diluted and undiluted samples (by EPA Sample Number) and
all dilutions and volumes used to obtain the reported
values. (If the volumes and dilutions are consistent for
all samples in a given SDG, a general statement outlining
these parameters may be reported in the SDG Narrative).
5) Duplicates.
6) Spikes (indicating standard solutions used, final spike
concentrations, volumes involved). If spike information
(source, concentration, volume) is consistent for a given
SDG, a general statement outlining these parameters may be
reported in the SDG Narrative).
7) Instrument used, any instrument adjustments, data
corrections or other apparent anomalies in the measurement
B-8 10/91
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record, including all data voided or data not used to
obtain reported values and a brief written explanation in
the SOG Narrative.
8) All information, for HYICP, Flame AA, and .Furnace AA
analysis, clearly and sequentially identified in the raw
data, including EPA Sample Number and date of analysis,
sample and analytical spike data, percent recovery,
coefficient of variation, full MSA data, MSA correlation
coefficient, slope and y intercept of linear fit, f JiaJ
sample concentration (standard addition concentratio. •,
9) All ICP/MS tuning and mass calibration data, in addition
to all internal standard results including the elements
and concentration used.
10) All retention time data for Ion Chromatography.
11) Time and date of each and every analysis. Instrument run
logs may be submitted if they contain this information.
If the instrument does not automatically provide times of
analysis, they shall be entered manually on all raw data
for initial and continuing calibration verification and
blanks, as well as on data for tuning solutions, CRDL
standards, interference check samples and the linear range
standard.
12) Integration tines for all analyses.
d. Preparation Logs
Preparation Logs shall be submitted in the following order:
ICP, ICP/MS. HYICP, Flame AA, Furnace AA, Mercury. Cyanide,
Fluoride, and N02/N03-N. These logs shall include: (1)
preparation date, (2) sample volume, (3) sufficient information
to unequivocally identify which QC samples (i.e. , laboratory
control sample, preparation blank) correspond to each batch
prepared, (4) comments describing any significant sample
changes or reactions that occurred during preparation, and (5)
report pH <2 or >12, as applicable.
3. A copy of the Sample Traffic Report and Cover Sheet submitted in
Item C for all of the samples in the SDG. The Traffic Reports shall
be arranged in increasing EPA Sample Number order, considering both
alpha and numeric designations.
D. Data in Computer-Readable Form
The Contractor shall provide a computer-readable copy of the data on
data reporting Forms I-XVIII for all samples in the Sample Delivery
Group, as specified in the Contract Performance/Delivery Schedule.
Computer-readable data deliverables shall be submitted on an IBM or IBM-
compatible, 5.25 inch floppy double-sided, double density 360 K-byte or
a high density 1.2 M-byte diskette or on an IBM or IBM-compatible, 3.5
B-9 10/91
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inch double-sided, double density 720 K-byte or a high density 1.44 M-
byte diskette. The data shall be recorded in ASCII, text file format,
and shall adhere to the file, record and field specifications listed in
Exhibit H.
When subnitted, diskettes shall be packaged and shipped in such a manner
that the diskette(s) cannot be bent or folded, and will not be exposed
to extreme heat or cold or any type of electromagnetic radiation. The
diskette(s) must be included in the same shipment as the hardeopy data
and shall, at a minimum, be enclosed in a diskette mailer.
Complete SPG File (CSF)
As specified in the Delivery Schedule, one Complete SDG File, including
the original Sample Data Package, shall be delivered to the Region
concurrently with delivery of copies of the Sample Data Package to SMO
and EMSL/LV. The contents of the CSF will be numbered according to the
specifications described in Section III and IV of Exhibit B. The
Document Inventory Sheet, Form DC-2, is contained in Section IV. The
CSF will contain all original documents where possible. No copies of
original documents will be placed in the CSF unless the originals are
bound in a logbook maintained by the laboratory. The CSF will contain
all original documents specified in Section III and IV, and Form DC-2 of
Exhibit B.
The CSF will consist of the following original documents in addition to
the documents in the Sample Data Package:
1. Original Sample Data Package (See Exhibit B, Item C)
2. A completed and signed Document Inventory Sheet (Form DC-2)
3. All original shipping documents including, but not limited to, the
following documents:
a. EPA Chain-of-Custody Record.
b. Airbills.
c. EPA (SMO) Traffic Reports.
d. Sample Tags (if present) sealed in plastic bags.
4. All original receiving documents including, but not limited to, the
following documents:
a. Form DC-1.
b. Other receiving forms or copies of receiving logbooks.
c. SDG Cover Sheet.
5. All original laboratory records of sample transfer, preparation, and
analysis including, but not limited to, the following documents:
B-10 10/91
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a. Original preparation and analysis forms or copies of
preparation and analysis logbook pages.
b. Internal sample and sample extract transfer chain-of-custody
records.
c. All instrument output, including strip charts from screening
activities.
6. All other original case-specific documents in the possession of the
laboratory including, but not limited to, the following documents:
a. Telephone contact logs.
b. Copies of personal logbook pages.
c. All handwritten Case-specific notes.
d. Any other Case-specific documents not covered by the above.
NOTE: All Case-related documentation may be used or admitted as
evidence in subsequent legal proceedings. Any other Case-specific
documents generated after the CSF is sent, as well as copies that
are altered in any fashion, are also deliverables (original to the
Region and copies to SMO and EMSL/LV).
If the laboratory does submit Case-specific documents after
submission of the CSF, the documents should be numbered as an
addendum to the CSF and a revised DC-2 Form should be submitted; or
the documents should be numbered as a new CSF and a new DC-2 Form
should be submitted to the Region only.
F. Quarterly/Annual Verification of Instri't||«»'"f Parj>ineters
The Contractor shall perform and report quarterly/annual verification of
instrument detection limits by methods specified in Exhibit E for each
instrument used under this contract. For the ICP and ICP/MS
instrumentation, the Contractor shall also perform and report annually
interelement correction factors (including method of determination),
wavelengths and masses used and integration times. Forms for
Quarterly/Annual Verification of Instrument Parameters for the current
year shall be submitted in each SDG data package, on Forms XII and XIII
as specified in Section III of this Exhibit. Submission of
Quarterly/Annual Verification of Instrument Parameters shall include the
raw data used to determine those values reported.
Analytical results and QC for the method reference sample analysis, as
specified in Exhibit E, shall be tabulated on Form IX.
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H. Results of Performance Evaluation Safflple (PES)
Analytical results for the PES analysis, as specified in Exhibit E,
shall be tabulated on Form I.
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Table 1
Codes for Labeline DaCa
Sanple XXXXXX
Duplicate JUUULXAU
Matrix Spike XXXXXXS
Serial Dilution JUUUtxXju
Analytical Spike JOUtxXXA
Post Digestion/Distillation Spike XXXXXXA
MSA:
Zero Addition XXXxXXO
First Addition XXXXXX1
Second Addition XXXXXX2
Third Addition XXXXXX3
Instrument Calibration Standards:
1C? S or SO for blank standard
Atonic Absorption and Cyanide SO, S10,...etc.
Initial Calibration Verification ICV
Initial Calibration Blank ICB
Continuing Calibration Verification CCV
Continuing Calibration Blank CCB
Interference Check Samples:
Solution A ICSA
Solution AB ICSAB
CRDL Standard CRI
Laboratory Control Samples LCS
Preparation Blank • PBV
Linear Range Analysis Standard LRS
Memory Test Solution UTS
Tuning Solution TS
Notes:
1. When an analytical spike or MSA is performed on samples other than field
samples, the "A", "0", "1", "2" or "3" suffixes must be the last to be
added to the EPA Sample Number. For instance, an analytical spike of a
duplicate must be formatted "XXXXXXDA".
2. The numeric suffix that follows the "S" suffix for the standards
indicates the true value of the concentration of the standard in ug/L.
3. ICF calibration standards usually consist of several analytes at
different concentrations. Therefore, no numeric suffix can follow the
ICP calibration standards unless all the analytes in the standard are
prepared at the same concentrations. For instance, the blank for ICP
must be formatted "SO".
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SECTION III
FORM INSTRUCTION GUISE
This section contains specific instructions for the coupletion of all
required Inorganic Data Reporting Forms. This section is organized into the
following Parts:
A. General Information and Header InforaatiGu-
B. Cover Page - [COVER PAGE - LCIN]
C. Analysis Data Sheet [FORM I - LCIN]
D. Initial and Continuing Calibration Verification [FORM II - LCIN]
E. CRDL Standards [FORM III - LCIN]
F. Linear Range Standards [FORM IV - LCIN]
G. Blanks [FORM V - LCIN]
H. ICP and ICP/MS Interference Check Sample [FORM VI- LCIN]
I. Spike Sample Recovery [FORM VII - LCIN]
J. Duplicates [FORM VIII - LCIN]
K. Laboratory Control Sample [FORM IX - LCIN]
L. Serial Dilution [FORM X - LCIN]
M. Standard Addition Results [FORM XI - LCIN]
N. Instrument Detection Limits [FORM XII - LCIN]
0. ICP and ICP/MS Interelement Correction Factors [FORM XIII - LCIN]
P. ICP and ICP/MS Tuning and Response Factor Criteria [FORM XTV -
LCIN]
Q. ICP/MS Internal Standards Summary [FORM XV - LCIN]
R. Analysis Run Log (A) [FORM XVI - LCIN]
S. Analysis Run Log (B) [FORM XVII - LCIN]
T. Standard Solutions Sources [FORM XVIII - LCIN]
U. Sample Log-In Sheet [Form DC-1]
V. Document Inventory Sheet [Form DC-2]
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A.
General Information and Header Information
Values must be reported on the hardcopy data reporting fonts according
to the individual form instructions in this Section. Each fora
submitted must be filled out completely for all analytes and samples
before proceeding to the next form of the same type. Multiple forms
cannot be submitted in place of one form if the information on those
forms can be submitted on one form.
All characters that appear on the data reporting forms presented in the
contract (Exhibit B, Section IV) must be reproduced by the Contractor
when submitting data, and the format of the foxas submitted oust be
identical to that shown in the contract. Mo information may be added,
deleted, or moved from its specified position without prior written
approval of Sift}. The names of the various fields and analytes (i.e. ,
•Lab Code", "Aluminum") must appear as they do on the forms in the
contract, including the options specified in the form.
Six pieces of information are common to the header sections of each data
reporting form. These are: Lab Name, Contract, Lab Code, Case No., SAS
No., and SDG No. This information must be entered on every form and
must match on all forms.
The "Lab Name" must be the name chosen by the Contractor to identify the
laboratory. It may not exceed 25 characters.
The "Contract" is the number of the contract, including the hyphens,
under which the analyses were performed.
The "Lab Code" is an alphabetic code of up to 6 characters, assigned by
SMO, to identify the laboratory and aid in data processing. This lab
code shall be assigned by SMO at the time a contract is awarded, and
must not be modified by the Contractor, except at the direction of SMO.
The "Case No." is the SMO-assigned Case number (5 spaces
associated with the sample and reported on the Traffic Report.
The "SAS No." is (where applicable) the SMO-assigned number for analyses
performed under Special Analytical Services. If samples are to be
analyzed under SAS only, and reported on these forms, then enter SAS No.
and leave Case No. blank. If samples are analyzed according to a
Routine Analytical Services Protocol and have additional SAS
requirements, list both Case No. and SAS No. on all forms. If the
analyses have no SAS requirements, leave "SAS No." blank. (NOTE: Some
samples in an SDG may have a SAS No., while others do not.)
The "SDG No." is the Sample Delivery Group (SDG) number. The SDG number
is the EPA Sample Number of the first sample received in the SDG. When
several samples are received together in the first SDG shipment, the SDG
number must be the lowest sample number (considering both alpha and
numeric designations) in the first group of samples received under the
SDG.
The other information common to several of the forms is the "EPA Sample
No.". This number appears either in the upper right-hand corner of the
B-15 10/91
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font, -or as the left column of a cable suonarizing data from a nuaber of
samples. When "EPA Sample No.* is entered into the triple-spaced box in
the upper right-hand corner of a form, it must be centered on the middle
line of the three lines that comprise the box.
All field samples and quality control samples must be identified with an
EPA Sample Number. For field samples, the EPA Sample Number is the
unique identifying number given in the Traffic Report that accompanied
that sample. The quality control samples abbreviations listed in Table
1 must be used as appropriate.
The Form Suffix for each Form must appear in the two character space
provided after the form number in the bottom section of the Fora. The
Form Suffix is used to sequentially distinguish between different forms
of the same type (Form Number). No two Forms of the same type may have
the same Form Suffix (see Exhibit H).
All the values substituted in the formulas given in the forme
instructions must be exactly those values reported on the form for which
the formula applies.
All results must be transcribed to Forms II-XVIII from the raw data to
the specified number of decimal places that are described in Exhibit B
and Exhibit H. The raw data result is to be rounded only when the
number of figures in the raw data result exceeds the •••»<••»• number of
figures specified for that result entry on that form. If there are not
enough figures in the raw data result to enter in the specified space
for that result, then zeros must be used for decimal places to the
specified number of reporting decimals for that result for a specific
form. The following examples of floating decimal places are provided:
Fflu Data Result
5.9
5.99653
95.99653
995.99653
9995.996
99995.9
999995.9
Soecified Forw^t
6
6
6
6
6
6
6
.3
.3
.3
.3
.3
.3
.3
(to
(to
(to
(to
(to
(to
(to
three
three
three
three
three
three
three
decimal
decimal
decimal
decimal
decimal
decimal
decimal
Correct Entrv on Form
places)
places)
places)
places)
places)
places)
places)
5.900
5.997
95 . 997
996.00
9996.0
99996.
invalid
For rounding off numbers to the appropriate level of precision, observe
the following common rules. If the figure following those to be
retained is less than 5, drop it (round down). If the figure is greater
than 5, drop it and increase the last digit to be retained by 1 (round
up). If the figure following the last digit to be retained equals 5 and
there are no digits to the right of the 5 or all digits to the right of
the 5 equal zero, then round up if the digit to be retained is odd, or
round down if that digit is even. See also Rounding Rules entry in
Glossary (Exhibit G).
Before evaluating a number for being in control or out of control of a
certain limit, the number evaluated must be rounded using EPA rounding
rules to the significance reported for that limit. For instance, the
control limit for an ICV is plus or minus 10% of the true value. A
percent recovery value of 110.4 would be considered in control while a
B-16 10/91
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value of 110.6 would be considered out of control. In addition, a value
of 110.50 would be in control while a value of 110.51 would be out of
control.
B. Cover Page [Cover Page - LCIN]
This font is used to list all field samples, duplicates, spikes, and
perfomance evaluation sanples analyzed within a Saople Delivery Group,
and to provide certain analytical info mat ion and general consents. It
is also the document that is signed by the Laboracory Manager to
authorize and release all data and deliverables associated with the SDG.
Complete the header information according to the instructions in Part A
and as follows.
The "SOW No." is the SMO-designated number Chat indicates Che version of
Che method under which analyses in the data package have been performed.
For samples analyzed using this method, enter "10/91" for "SOW Mo."
Under "EPA Sample No.", enter the EPA Sample No. of each field sample,
(including spikes, duplicates, and the PE sample) to eight spaces, that
required analysis within the SDG. Spikes must contain an "S" suffix and
duplicates a "D" suffix. These sample numbers must be listed on Che
form in ascending alphanumeric order using Che EBCDIC convention. Thus,
if MAB123 is the lowest (considering both alpha and numeric characters)
EPA Sample No. within the SDG, it would be entered in the first EPA
Sample No. field. Samples would be listed below it, in ascending
sequence - MAB124, MAB125, MAC111, MAllll, MAllllD, MA1111S, etc.
All EPA Sample Nos. must be listed in ascending alphanumeric order,
continuing to Che following Cover Page if applicable.
Under "Lab Sample ID.", a Lab Sample ID. (Co ten spaces) may be entered
for each EPA Sample No. If a Lab Sample ID is entered, it must be
entered identically (for each EPA Sample No.) on all associated data.
Enter "YES* or "NO" in answer to each of the two questions concerning
ICP and ICP/MS corrections. Each question must be explicitly answered
with a. "YES" or a "NO". The third question must be answered with a
"YES" or "NO" if the answer to the second question is "YES". It should
be left blank if the answer to the second question is "NO".
Under "Comments", enter any statements relevant Co the analyses
performed under the SDG as a whole.
Each Cover Page must be signed, in original, by the Laboratory Manager
or the Manager's designee and dated, to authorize the release and verify
the contents of all data and deliverables associated with an SDG.
For "Name", enter the first and last name (to 25 spaces) of the person
whose signature appears on the Cover Page.
B-17 10/91
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For "Date*, enter the date (formatted MM/DD/YY) on which the Cover Page
is signed.
For "Title", enter the title (to 25 spaces) of the person whose
signature appears on the Cover Page.
C. AMJy»i« Data Sheet [Fora I - LCXN]
This form is used to tabulate and report sample analysis results for
target analytes (Exhibit C).
Complete the header information according to the instructions in Part A
and as follows.
For "Lab Sample 10", enter the laboratory sample ID for the EPA sample
number listed on the form if one was designated, as listed on the Cover
Page.
"Date Received* is the date (formatted MM/DD/YY) of sample receipt at
the laboratory, as recorded on the Traffic Report, i.e., the Validated
Time of Sample Receipt (VTSR).
Under the column labeled "Concentration", enter for each analyte either
the value of the result (if the concentration is greater than or equal
to the Instrument Detection Limit), or the value of the Instrument
Detection Limit for the analyte corrected for any dilutions (if the
concentration is less than the Instrument Detection Limit).
Analytical results must be reported to two significant figures if the
result value is less than 10; to three significant figures if the result
value is greater than or equal to 10. NOTE: This requirement for
reporting results to two or three significant figures applies to Form I-
LCIN only. Follow the specific instructions for reporting all other
results on required forms as described in this exhibit.
Under the columns labeled "C", "Q" , and "M*, enter result qualifiers as
identified below. If additional qualifiers are used, their explicit
definitions must be included on the Cover Page in the Comments section.
Form I includes fields for three types of result qualifiers. These
qualifiers must be completed as follows:
o C (Concentration) qualifier -- Enter "U" if the reported value was
obtained from a reading that was less than the Instrument Detection
Limit (IDL).
o Q qualifier -- Specified entries and their meanings are as follows:
E - The reported value is estimated because of the presence of
interference.
M - Duplicate injection (exposure) precision not met.
N - Spiked sample recovery not within control limits.
B-18 10/91
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3 - The reported value was determined by the Method of Standard
Additions (MSA).
* - Duplicate analysis not within control limits.
+ - Correlation coefficient for the MSA is less than 0.995.
Entering "E", "S", or "+" is mutually exclusive. Ho combination of
these qualifiers can appear in the same field for an analyte.
o M (Method) qualifier -- Enter:
- "P * for IvT.
"M " for 1C*,-•••'••••
•H " for HYICP
"F * for Graphite Furnace Atomic Absorption
"A " for Flame Atomic Absorption
"PM* for ICP when microwave digestion is used
"MM" for ICP/MS when microwave digestion is used
*HM" for HYICP when microwave digestion is used
"FM" for Graphite Furnace AA when microwave digestion is used
"AM" for Flame AA when microwave digestion is used
"CV- for Cold Vapor AA
"AV" for Automated Cold Vapor AA
•AS* for Semi-Automated Spectrophotometric
"C " for Manual Spectrophotometric
*CA" for Medi-distillation Spectrophotometric
"1C" for Ion Chromatography
"AC" for Automated Spectrophotometric
"IS* for Ion Selective Electrode (Potentiometrie)
"NR" if the analyte is not required to be analyzed
" " if no results for the analyte appear on the fora
A brief physical description of the sample before and after preparation
must be reported in the fields for Color. Clarity, and Viscosity. The
following descriptive terms are required:
Color - red, blue, yellow, green, orange, violet, white,
colorless, brown, grey, or black
Clarity - clear, cloudy, or opaque
Viscosity - nonviscous or viscous
Mote any significant changes that occur during sample preparation (i.e.,
emulsion formation) in the Comments field. Enter any sample-specific
comments concerning the analyte results in the Comments field.
Initial and Continuing Calibration Verification [Font II - HCIH]
This fora is used to report analyte recoveries from calibration
solutions.
Complete the header information according to the instructions in Part A
and as follows.
Under "WOMN", enter the number of the wavelength or mass number for
which the results of each analyte are reported on the Form. The
Wavelength or Mass Number is a. number assigned to each wavelength (mass
or detector configuration for ICP/MS) used when more than one wavelength
B-19 10/91
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(mass or detector configuration for ICP/MS) is used to obtain data for
an analyte in the SDG. A wavelength number of "1* is assigned to the
longest wavelength used for the analyte in the SDG. A wavelength number
of "2" is assigned to the second longest wavelength and so on. A mass
number of "1" is assigned to the greatest mass or the most sensitive
detector configuration of the same mass used for the analyte in the SDG.
A mass number "2" is assigned to the second greatest mass or the less
sensitive detector configuration of the same mass and so on. The field
must be left blank if a single wavelength (or mass for ICP/MS) is used
to obtain data for an analyte in the SDG.
Under "Initial Calibration True", enter the value (in ug/L, to two
decimal places) of the concentration of each analyte in the Initial
Calibration Verification Solucion. If the analyte is not analyzed for,
leave the field empty.
Under 'Initial Calibration Found", enter the most recent value (in ug/L,
to three decimal places), of the concentration of each analyte measured
in the Initial Calibration Verification Solution.
Under "Initial Calibration %R", enter the value (to the nearest whole
number) of the percent recovery computed according to the following
equation:
Found(ICV)
%R - x 100
True(ICV)
Where, True (ICV) is the true concentration of the analyte in the Initial
Calibration Verification Solution and Found(ICV) is the found
concentration of the analyte in the Initial Calibration Verification
Solution.
Under "Continuing Calibration True", enter the value (in ug/L, to two
decimal place) of the concentration of each analyte in the Continuing
Calibration Verification Solution. If the analyte is not analyzed for,
leave the field empty.
Under "Continuing Calibration Found", enter the value (in ug/L,' to three
decimal places) of the concentration of each analyte measured in the
Continuing Calibration Verification Solution.
Note that the fora contains two "Continuing Calibration Found* columns.
The column to the left must contain values for the first Continuing
Calibration Verification, and the column to the right must contain
values for the second Continuing Calibration Verification. The column
to the right should be left blank if no second Continuing Calibration
Verification was performed during the run.
If more than one Form II is required to report multiple Continuing
Calibration Verifications, then the column to the left on the second
form must contain values for the third Continuing Calibration
Verification, the column to the right must contain values for the fourth
Continuing Calibration Verification, and so on.
B-20 10/91
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Under "Continuing Calibration %R", enter the value (to the nearest -hole
number) of the percent recovery computed according to the following
equation:
Found(CCV)
%R - x 100
True(CCV)
where, True(CCV) is the true concentration of each analyte, and
Found(CCV) is the found concentration of the analyte in the Continuing
Calibration Verification Solution.
Note that the fora contains two "Continuing Calibration %R" columns.
Entries to these columns oust follow the sequence detailed above for
entries to the "Continuing Calibration Found" columns.
Under "M", enter the method used, as explained in Part C.
If more than one wavelength or elemental expression is used to analyze
an analyte, submit additional Forms II as appropriate.
The order of reporting ICVs and CCVs for each analyte must follow the
temporal, order in which the standards were run starting with the first
Form II and moving from the left to the right continuing to the
following Forms II as appropriate. For instance, the first ICV for all
analytes must be reported on the first Form II. In a run where three
CCVs were analyzed, the first CCV must be reported in the left CCV
column on the first Form II and the second CCV must be reported in the
right column of the same fora. The third CCV must be reported in the
left CCV column of the second Form II. On the second Form II, the ICV
column and the right CCV column must be left empty in this example. In
the previous example, if a second run for an analyte was needed, the ICV
of that run must be reported on a third Form II and the CCVs follow in
the same fashion as explained before.
In the case where more than one wavelength or elemental expression is
used for an analyte in the SDG, all ICV and CCV results of the longest
wavelength, greatest mass, or most sensitive detector configuration from
all runs must be reported before proceeding to report the results of the
second longest wavelength, the second greatest, uutss, or less sensitive
detector configuration used, and so on.
E. CRPL Standards [Form III - LCIN]
This form is used to report analyte recoveries from analyses of the CRDL
Standards.
Complete the header information according to the instructions in Part A
and as follows.
Under "WOMN" , enter the wavelength or mass number as explained in Part
B-21 10/91
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Under "Initial True", encer the value (in ug/L, to two decimal places)
of Che concentration of each analyte in the CRDL Standard Source
Solution that was analyzed for analytical sanples associated with the
SDG.
Under "Initial Found", enter the value (in ug/L, to three decimal
places) of the concentration of each analyte measured in the CRDL
Standard Solution analyzed at the beginning of each run.
Under "Initial %R", enter the value (to the nearest whole number) of the
percent recovery computed according to the following equation:
CRDL Standard Initial Found
%R - — x 100
CRDL Standard True
Under "Final Found", enter the value (in ug/L, to three decimal places)
of the concentration of each analyte measured in the CRDL Standard
Solution analyzed at the end of each run.
Under "Final %R", enter the value (to the nearest whole number) of the
percent recovery computed according to the following equation:
CRDL Standard Final Found
%R - ——• x 100
CRDL Standard True
Note that for every initial solution reported there must be a final one.
However, the opposite is not true. If a CRDL Standard was required to
be analyzed in the middle of a run (to avoid exceeding the 8-hour
limit), it must be reported in the "Final Found1* section of this form.
Under "M", enter the method used, as explained in Part C.
If more CRDL standards analyses were required or analyses were perfo
using more than one wavelength or elemental expression per analyte,
submit additional Forms III in the order explained in Fart D as
appropriate.
The order of reporting CRDL standards for each analyte must follow the
temporal order in which the standards were run starting with the first
Fora III and continuing to the following Forms III as appropriate. When
multiple wavelengths or elemental expressions are used for one analyte,
all the results of the longer wavelength or elemental expressions must
be reported before proceeding to the next wavelength or elemental
expression.
F. Linear Range Standards (LRS) [Fora IV - LCIN]
This form is used to report analyte recoveries from analyses of the
Linear Range Standards (LRS).
Complete the header information according to the instructions in Part A
and as follows.
B-22 10/91
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Under "WOMN", enter the wavelength or mass number as explained in Part
D.
Under "Initial True", enter the value (in ug/L, to two decimal places)
of the concentration of each analyte in the LRS Standard Source
Solution that was analyzed for analytical samples associated with the
SDG.
Under "Initial Found", enter the value (in ug/L. to three decimal
places) of the concentration of each analyte measured in the LRS
Standard Solution analyzed at the beginning of each run.
Under "Initial %R", enter the value (to the nearest whole number) of
the percent recovery computed according to the following equation:
.LRS Standard Initial Found
%R - x 100
LRS Standard True
Under "Final Found", enter the value (in ug/L, to three decimal places)
of the concentration of each analyte measured in the LRS Standard
Solution analyzed at the end of each run.
Under "Final %R", enter the value (to the nearest whole number) of the
percent recovery computed according to the following equation:
LRS Standard Final Found
%R - x 100
LRS Standard True
Note that for every initial solution reported there must be a final
one. However, the opposite is not true. If a LRS Standard was
required to be analyzed in the middle of a run (to avoid exceeding the
8-hour limit), it must be reported in the "Final Found" section of this
form.
Under "M", enter the method used, as explained in Part C.
If more LRS standards analyses were required or analyses were performed
using more than one wavelength or elemental expression per analyte,
submit additional Forms IV in the order explained in Part D as
appropriate.
The order of reporting LRS standards for each analyte must follow the
temporal order in which the standards were run starting with the first
Form IV and continuing to the following Forms IV as appropriate. When
multiple wavelengths or elemental expressions are used for one analyte,
all the results of one wavelength or elemental expression must be
reported before proceeding to the next wavelength.
B-23 10/91
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G. Blanks (Font V - LOIN]
This fora is used to report analyte concentrations found in the Initial
Calibration Blank (ICB), in Continuing Calibration Blanks (CCB), and in
the Preparation Blank (PB).
Complete the header infomation according to the instructions in Part A
and as follows.
Under "WOMN", enter the wavelength or mass number as explained in Part
/'<.
Under "Im.c>'al Calib. Blank", enter the concentration (in ug/L, to three
decimal places) of each analyte in the most recent Initial Calibration
Blank.
Under the "C" qualifier field, for any analyte enter "U" if the absolute
value of the analyte in the blank is less than the IOL.
Under "Continuing Calibration Blank 1", enter the concentration (in
ug/L, to three decimal places) of each analyte detected in the first
required Continuing Calibration Blank (CCB) analyzed after the Initial
Calibration Blank. Enter any appropriate qualifier, as explained for
the "Initial Calibration Blank," to the "C" qualifier column immediately
following the "Continuing Calibration Blank 1" column.
If only one Continuing Calibration Blank was analyzed, then leave the
columns labeled "2" and "3* blank. If two additional CCBs were
analyzed, complete the columns labeled "2" and "3", in accordance with
the instructions for the "Continuing Calibration Blank 1" column. If
more than two Continuing Calibration Blanks were analyzed, then complete
additional Forms V as appropriate.
Under "Preparation Blank", enter the concentration (in ug/L, to three
decimal places) of each analyte in the Preparation Blank. Enter any
appropriate qualifier, as explained for the "Initial Calibration Blank,"
to the "C" qualifier column immediately following the "Preparation
Blank" column.
For all blanks, enter the concentration of each analyte (positive or
negative) measured above the IDL or below the negative value of the IDL.
Under "M", enter the method used, as explained in Part C.
If more than one wavelength or elemental expression is used to analyze
an analyte, submit additional Forms V as appropriate.
The order of reporting ICBs and CCBs for each analyte must follow the
temporal order in which the blanks were run starting with the first Form
V and moving from left to right and continuing to the following Forms V
as explained in Part D. When multiple wavelengths or elemental
B-24 j.o/91
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; 7 -
expressions are used for the analysis of one analyte, all Che results of
the longer wavelength, greater mass, or more sensitive detector
configuration must be reported before proceeding to the next wavelength
or elemental expression.
H. ICP AMD ICP/MS Interference Check Sample [Fora 71 - LCIH]
This form is used to report Interference Check Sample (ICS) results for
each ICP instrument used in Sample Delivery Group analyses.
Complete the header information according to the instructions in Part A
and as follows.
For "Instrument ID Number", enter an identifier that uniquely identifies
a specific instrument within the Contractor laboratory. Mo two
Instruments within a laboratory may have the same Instrument ID Number.
Under "WOMN", enter the wavelength or mass number as explained in Part
D.
Under "True Sol. A", enter the true concentration (in ug/L, to two
decimal places) of each analyte analyzed by ICP that is present in
Solution A. A concentration of zero "0" must be entered for the
analytes analyzed by ICP or ICP/MS that have no true value.
Under "True Sol. AB", enter the true concentration (in ug/L, to two
decimal places) of each analyte present in Solution AB. A concentration
of zero "0* must be entered for the analytes analyzed by ICP or ICP/MS
that have no true value.
Under "Initial Found Sol. A", enter the concentration (in ug/L, to three
decimal places) of each analyte analyzed by ICF that resulted from the
initial analysis of Solution A as required in Exhibit E.
Under "Initial Found Sol. AB", enter the concentration (in ug/L, to
three decimal places) of each analyte analyzed by ICP that resulted from
the initial analysis of Solution AB as required in Exhibit E.
Under "Initial Found %R" , enter the value (to the nearest whole number)
of the percent recovery computed according to the following equation:
Initial Found Solution AB
%R - x 100
True Solution AB
Leave the field empty is True Solution AB is equal to zero.
Under "Final Found Sol. A", enter the concentration (in ug/L, to three
decimal places) of each analyte analyzed by ICP that resulted from the
final analysis of Solution A as required in Exhibit E.
Under "Final Found Sol. AB", enter the concentration (in ug/L, to three
decimal places) of each analyte analyzed by ICP that resulted from the
final analysis of Solution AB as*required in Exhibit E.
B-25 10/91
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Under "Final Found %R", enter the value (Co ehe nearest whole number) of
the percent recovery computed according to the following equation:
Final Found Solution AB
%R - x 100
True Solution AB
Leave the field empty if True Solution AB is equal to zero.
For All Found values of solutions A and AB, enter the concentration
(positive, negative, or zero) of each analyte at each wavelength nr
elemental expression used for analysis by the instrument.
Note that for every initial solution reported there must be a final one.
However, the opposite is not true. If an ICS was required to be
analyzed in the middle of a run (to avoid exceeding the 8-hour limit) ,
it must be reported in the "Final Found" section of this fora.
Under "M", enter the method used, as explained in Part C.
If more ICS analyses were required, submit additional Forms VI as
appropriate.
The order of reporting ICSs for each analyte must follow the temporal
order in which the standards were run starting with the first Form VI
and continuing to the following Forms VI as appropriate. When multiple
wavelengths or elemental expressions are used for one analyte, all the
results of longer wavelength, greater mass, or more sensitive detector
configuration must be reported before proceeding to the next wavelength
or elemental expression in the same manner as described in Part D.
I- Spike Sample Recovery [Form VII - LCIN]
This form is used to report results for the matrix spike.
Complete the header information according to the instructions in Part A
and as follows.
In the "EPA Sample No." box, enter the EPA Sample Number (8 places
maximum) of the sample from which the spike results on this form were
obtained. The number must be centered in the box.
Under "WOMN", enter the wavelength or mass number as explained in Part
D.
Under "Control Limit %R" , enter "75-125" if the spike added value was
greater than or equal to one-fourth of the sample result value. If not,
leave the field empty.
Under "Sample Result (SR)", enter the value (in ug/L, to three decimal
places), of the concentration for each analyte in the sample (reported
in the EPA Sample No. box) on which the matrix spike was performed.
Enter the IDL value if the analyte was not detected. Enter any
appropriate qualifier, as explained in Part C, to the "C" qualifier
column immediately following the "Sample Result (SR)" column.
B-26 10/91
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Under "Spiked Sample Result (SSR)", enter Che value (in ug/L, to three
.decimal places), of the concentration for each analyte in the matrix
spike saaple. Enter the IDL value if the analyte was not detected.
Enter any appropriate qualifier, as explained in Part C, to the "C*
qualifier column immediately following the "Spiked Sample Result (SSR)"
column.
Under "Spike Added (SA)", enter the value (in ug/L, to three decimal
places) of the concentration of each analyte added to the sample. If
the "Spike Added* concentration is specified in the contract, the value
added and reported must be that specific concentration in ug/L.
Under "%R", enter the value (to the nearest whole number) of the percent
recovery for all spiked analytes computed according to the following
equation:
(SSR - SR)
%R - x 100
SA
%R must be reported, whether it is negative, positive or zero.
A value of zero must be used for SSR or SR if the analyte value is less
than the IDL.
Under "Q", enter "N" if the Spike Recovery (%R) is out of the control
limits (75-125) and the Spike Added (SA) is greater than or equal to
one-fourth of the Sample Result (SR).
Under "M", enter method used as explained in Part C.
If different samples were used for spike sample analysis of different
analytes, additional Forms VII must be 'submitted for each sample as
appropriate.
Use additional Forms VII for each sample on which a required spike
sample analysis was performed.
J. Duplicates [Form VIII - LCIN]
The duplicates form is used to report results of duplicate analyses.
Complete the header information according to the instructions in Part A
and as follows.
In the "EPA Sample No." box, enter the EPA Sample Number (8 places
maximum) of the sample from which the duplicate results on this form
were obtained. The number must be centered in the box.
Under "WOMN", enter the wavelength or mass number as explained in Part
D.
B-27 10/91
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Under "Control Limit", enter the numerical value of the IOL (in ug/L, to
two decimal places) for the analyte if the sample or duplicate values
were less than Sx IDL. If both the sample and duplicate values were
less than the IDL or both were greater than or equal to Sx IDL, leave
the field empty.
Under 'Sample (S)", enter the original value (in ug/L, to three decimal
places) of the concentration of each analyte in the sample (reported in
the EPA Sample No. box) on which a duplicate analysis was performed.
Enter the IDL value if the analyte was not detected. Enter any
appropriate qualifier, as explained in Part C, to the "C" qualifier
column immediately following the "Sample (S)" column.
Under "Duplicate (D)", enter the value (in ug/L, to three decimal
places) of each analyte in the Duplicate sample (reported in the EPA
Sample No. box). Enter the IDL value if the analyte was not detected.
Enter any appropriate qualifier, as explained in Part C, to the "C"
qualifier column immediately following the "Duplicate (D)" column.
Under "RPD", enter the absolute value (to the nearest; whole number) of
the Relative Percent Difference for all analytes detected above the IDL
in either the sample or the duplicate, computed according to the
following equation:
IS - D|
RPD - x 100
(S + D)/2
A value of zero must be substituted for S or D if the analyte
concentration is less than the IDL in either one. If the analyte
concentration is less than the IDL in both S and D, leave the RPD field
empty.
Under "Q", enter "*" if the duplicate analysis for the analyte is out of
control. If both sample and duplicate values are greater than or equal
to Sx IDL, then the RPD must be less than or equal to 20% to be in
control. If either sample or duplicate values are less than Sx IDL,
then the absolute difference between the two values must be less than or
equal to the IDL to be in control. If both values are below the IDL,
then no control limit is applicable.
Under "M", enter method used as explained in Part C.
Use additional Forms VIII for each sample on which a required duplicate
sample analysis was performed.
K. laboratory Control Sample [Form IX - LCIH1
This form is used to report results for the Laboratory Control Sample.
Complete the header information according to the instructions in Part A
and as follows.
If no analytes were analyzed by a certain method or if the analyte was
not required to be analyzed then leave the appropriate spaces empty.
B-28 10/91
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Under "WOMN". enter the wavelength or mass number as explained in Part
D.
Under "Limits", enter the lower limit (in ug/L, to two decimal places)
in the left column, and the upper limit (in ug/L, to one decimal place)
in the right column for each analyte in the LCS Source solutions.
Under "True", enter the value (in ug/L, to two decimal places) of the
concentration of each analyte in the LCS Standard Source.
Under "Found", enter the measured concentration (in ug/L, to three
decimal places) of each analyte found in the LCS solutions. Enter the
IDL value if the analyte was not detected.
Under "C", enter "U" or leave empty, to describe the found value of the
LCS, as explained in Part C.
Under "%R", enter the value of the percent recovery (to the nearest
whole number) computed according to the following equation:
LCS Found
%R - x 100
LCS True
If the analyte concentration is less than the IOL, a value of zero must
be substituted for the LCS found.
Under "M", enter method used as explained in Part C.
Submit additional Forms IX as appropriate, if more than one LCS was
required. In addition, submit additional Forms IX if more than one
wavelength, mass, or method was used to determine an analyte for a
sample, as described in Part D:
L. Serial Dilution [Form X - LCIN]
The Serial Dilution Form is used to report results of serial dilution
analyses.
Complete the header information according to the instructions in Part A
and as follows.
In the "EPA Sample No." box, enter the EPA Sample Number (8 places
maximum) of the sample from which the duplicate results on this form
were obtained. The number must be centered in the box.
Under "WOMN", enter the wavelength or mass number as explained in Part
D.
Under "Initial Sample Result (I)", enter the measured value (in ug/L, to
three decimal places) of the concentration of each analyte in the
undiluted sample (reported in the EPA Sample No. box) on which a Serial
Dilution analysis was. jfer*ortned.' ^nt&r.che IDL value if the analyte
B-29
10/91
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was not decected. Encer any appropriate qualifier, as explained in Part
C, co the -C* qualifier column immediately following Che "Initial Sample
Result (I)" column.
Note chat the Initial Sample concentration for an analyte does not have
to equal Che value for ChaC analyte reported on Fora I. It is the value
of the analyte concentration (uncorrected for dilution) Chat is within
the linear range of the instrument.
Under "Serial Dilution Result (S)", enter Che measured concentration
value (in ug/L, to three decimal places) of each analyte in the serially
diluted sample (reported in Che EPA Sample No. box). Enter the IOL
. value multiplied by five if Che analyte was not detected. Enter any
appropriate qualifier, as explained in Part C, to Che "C" qualifier
column immediately following Che "Serial Dilution Result (S)" column.
Noce Chat che Serial Dilucion ResulC (S) is obtained by multiplying by
five the instrument measured value (in ug/L) of the serially diluted
sample. In addition, che "C" qualifier for che serial dilution must be
established based on che serial dilution resulc before correcting it for
Che dilution, regardless of che value reported on Che form.
Under "% Difference", enter che absolute value (Co Che nearest whole
number) of che percent difference in concentraCion of required analytes,.
between che inicial sample and che diluted sample (adjusted for
dilution) for all analytes detected above Che IDL in che sample,
computed according Co Che following equation:
|I • S|
RPD - x 100
I
A value of zero muse be substituted for S if che analyte concentraCion
is less Chan Che IDL. If che analyte concentration is less Chan Che IDL
in I, leave che "% Difference" field empty.
Under "Q", enter "E" if che % difference value is greater than 10% and
Che original sample concencracion reported on Form I is greater than SO
times the IDL.
Under "M", enter method used as explained in Part C.
Use additional Forms X for each sample on which a required serial
dilution analysis was performed.
M. Standard Addition Results [Form XI - LCIM]
This form is used to report the results of samples analyzed using che
Method of Standard Additions (MSA).
Complete the header information according to the instructions in Part A.
B-30 10/91
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Under "EPA Sample No.", -ncer Che EPA Sample Numbers (8 places maximum)
of all analytical samples analyzed using MSA. This includes reruns by
MSA (if the first MSA was out of control) as explained in Exhibit E.
A maximum of 32 samples can be entered on this form. If additional
samples required MSA, submit additional Forms XI. Samples must be
listed in alphanumeric order per analyte, continuing Co the next Form XI
if applicable.
Under "An", enter the chemical symbol (3 ipaces maximum) for each
analyte for which MSA was required for eac.- >wple listed. The analytes
must be in alphabetic listing of Che chemical symbols.
Results for different samples for each analyte must be reported
sequentially, with the analytes ordered according to Che alphabetic
listing of their chemical symbols. For instance, results for As
(arsenic) in samples MAAllO, MAAlll, and MAA112 would be reported in
sequence, followed by Che result for Pb (lead) in MAAllO etc.
Under "Zero Found" (y^), enter the measured value in absorbance or
intensicy units (Co three decimal places) for Che analyte before any
addition is performed.
Under "First Added" (X2), enter the final concentration in ug/L (to cwo
decimal places) of the analyte (excluding sample contribution) after the
first addition to the sample analyzed by MSA.
Under "Firsc Found* (y£), encer Che measured value in absorbance or
intensicy units (to cwo decimal places) for Che analyte in Che sample
solution spiked with Che first addition.
Under "Second Added* (X3), enter Che final concencration in ug/L (to Cwo
decimal places) of Che analyte (excluding sample contribution) after Che
second addicion Co the sample analyzed by MSA.
Under "Second Found" (y3), enter the measured value in absorbance or
intensity units (to three decimal places) for Che analyte in Che sample
solution spiked with the second addicion.
Under "Third Added" (x^), enter the final concentration in ug/L (to
three decimal places) of the analyte (excluding sample contribution)
after Che third addition to the sample analyzed by MSA.
Under "Third Found" (y4), enter the measured value in absorbance or
intensity units (to three decimal places) for the analyte in Che sample
solucion spiked with Che third addition.
Note chac "Zero Found", "First Found", "Second Found", and "Third Found"
must have Che same dilution factor.
Under "Final Cone.", enter the final analyte concentration (in ug/L, to
three decimal places) in the sample as determined by MSA computed
according to the following formula:
Final Cone. - - (x-intercept)
B-31 10/91
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X
Note Chat the final concentration of an analyte does not have to equal
the value for that analyte which is reported on Fora I for that sample.
Under "r", enter the correlation coefficient (to three decinal places)
that is obtained for the least squares regression line representing the
following points (x,y):(0.0, "Zero Found"), ("First Added", "First
Found"), ("Second Added", "Second Found"), ("Third Added", "Third
Found").
Note that the correlation coefficient oust be calculated using the
ordinary least squares linear regression (unweighted) according to the
following formula:
r 4 I xjyj - I *i I yi
l*.Z«i2- (Zxi)2]V2 [4£yi2_ ( I
Where, x^ - 0
Under "Q", enter "+" if r is less than 0.995. If r is greater than or
equal to 0.995, then leave the field empty.
Under "M", enter method used as explained in Part C.
This form documents the Instrument Detection Limits for each instrument
that the laboratory used to obtain data for the Sample Delivery Group.
Only the instrument and wavelengths used to generate data for the SDG
must be included.
Complete the header information according to the instructions in Part A
and as follows.
Enter the "Instrument ID Number" for each instrument used to produce
data for the SDG, as explained in Section H.
For "Method", enter the method of analysis as explained in Part C.
Enter the date (formatted MM/DD/YY) on which the IDL values were
determined for use. This date must not exceed any of the analysis dates
for that instrument in the SDG data package. Also, it must not precede
them by more than three calendar months.
Under "Wavelength or Mass Number (WOMN)", enter the wavelength or mass
number, as explained in Part D.
Under "Wavelength", enter the wavelength in nanometers (to two decimal
places) for each analyte for which an Instrument Detection Limit (IDL)
has been established and is listed in the IDL column. If more than one
wavelength is used for an analyte, use other Forms XII as appropriate
to report the Instrument Detection Limit.
Under "Mass", enter the mass to charge ratio (m/z, nominal unit mass)
for each analyte for which an Instrument Detection Limit (IDL) has been
B-32 10/91
-------
established and is listed in Che IOL column. If more than one mass to
charge ratio is used in Che elemental expression to provide
quancicacion, Chen the mass Co charge ratio listed should be Che
analyce's primary mass in che equation used for quancicacion. For
example, if che elemental expression for che firsC selenium (WOMN) is Se
- (1.0000)(m/z 78)-(0.1869)(m/z 76) Chen Che Bass reported should be 78.
If more Chan one mass Co charge ratio is used for an analyce, use
additional Forms XII as appropriate Co report the Instrument Detection
Limit.
Under "Integ. Time", enter che integration time (in seconds, to two
decimal places) used for each measurement taken from each instrument.
Under "Background, " enter the type of background correction used to
obcain Furnace AA daCa. Enter "BS" for Smith Hieftje, *BO* for
Deuterium Arc, or "BZ" for Zeeman background correction.
Under "CRDL", enter che ConCracC Required DeCection Li ait (in ug/L) , as
established in Exhibit C. If detection limics other Chan Chose listed
in Exhibit C were required such as in SAS analysis, Chose detection
limits become che CRDL. They muse be reported on chis form and used
anywhere else where CRDL is referenced.
Under "IDL", enter the Instrument Detection Limit (in ug/L) as
determined by the laboratory for each analyte analyzed by the instrument
for which che ID Number is listed on chis form. IDLs muse be reported
Co two significant figures if che IDL value is less Chan 100 and Co
significanc figures for values above or equal Co 100.
Use additional Forms XII if more instruments, wavelengths, or elemental
expressions are used.
Use the Comments section Co indicate alcernacive wavelengChs or masses
and Che conditions under which Chey are used.
0. TCP and TCP/MS Intereleaent Correction Factors [Form ZXZZ-LCZH]
This form documents for each ICP and ICP/MS instrument the interelement
correction factors applied by the Contractor to obtain data for che SDG.
Although che correction factors are determined annually (every 12
calendar months) , a copy of the results of the annual interelement
correction factors muse be included with each SDG data package on Form
XIII.
Complete che header information according to instructions in Part A and
as follows .
Enter the "Instrument ID Number" for each ICP and ICP/MS instrument used
to produce data for che SDG, as explained in Seccion H. If more Chan
one ICP inscrumenc is used, submit additional Forms XIII as appropriate.
B-33 10/91
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For "Method", enter the method of analysis (two characters maximal) for
which the preparations listed on the form were made. Use appropriate
method codes as specified in Part C.
Report the date (formatted as MM/DD/YY) on which these correction
factors were determined for use. This date must not exceed any of the
analysis dates reported for that instrument in the SDG data package.
Also, it must not precede them by more than 12 calendar months.
Under "Wavelength or Mass", list the wavelength (in nanometers, to two
decimal places) for ICP instruments, or the mass to charge ratio (m/z,
to nominal unit mass) for ICP/MS instruments for each analyte analyzed
by either one of the two instruments. If more than one wavelength or
mass is used, submit additional Forms XIII as appropriate.
Under ."Interelement Correction Factors For:", enter the chemical symbol
in the two-space header field provided to indicate the analyte for which
the corrections in that column were applied.
In the column, enter the correction factor (negative, positive or zero,
to seven decimal places, 10 spaces max 1.mm) for each corrected analyte
analyzed by ICP. If an analyte was not corrected for an analyte that is
listed in the header of a column, a zero must be entered to indicate
that the correction was determined to be zero.
Use additional Forms XIII as appropriate if correction factors for more
than five analytes were applied.
Columns of correction factors for analytes requiring interelement
correction must be entered left to right starting on Form XIII according
to the alphabetic order of their chemical symbols starting on the first
Form XIII and proceeding to the following Form XIII as appropriate.
ICP an«| ^cy/MS Tuning and Response Factor Criteria [Form nv - LCIH]
This form is used for reporting tuning, response factor, and mass
calibration verification results for each ICP/MS run used to report data
in the SDG.
Complete the header information according to the instructions in Part A
and as follows.
Enter the "Instrument ID Number" for the ICP/MS instrument used to
produce data on the form, as explained in Section H. A Form XIV must be
submitted for each ICP/MS analysis run in the SDG.
For "Run No.", enter the run number (two spaces maximum) from which the
information on the form was taken. The run number is a sequential
number for each instrument in the SDG that identifies the different
analytical runs that are performed on the same instrument. The first
run number for an instrument must be one, the second oust be two, and so
on.
B-34 10/91
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s
For "Method", enter the method code (two characters maximum) according
to the specifications in Part C.
For "Analysis Date" , enter the date (formatted MM/DD/YY) of analysis of
the initial tuning solution from which the information on the form was
taken.
For "Analysis Times. Initial", enter the time (in military format -
HHMM) of analysis of the initial tuning solution from which the
information on this form was taken.
For "Analysis Times, Final", enter the time (in military format - HHMM)
of analysis of the final tuning solution from which the information on
this form was taken.
Under "% Relative Abundance, Initial*, enter the percent relative
abundance (to two decimal places) calculated from the intensities
measured, for each of the isotopes listed, as a result of analyzing the
100 ppb tuning solution at the beginning of each ICP/MS run. The
isotopes are listed in the first column from the left in the Tuning
Section of the Form.
Under "% Relative Abundance, Final", enter the percent relative
abundance (to two decimal places) calculated from the intensities
measured, for each of the isotopes listed, as a result of analyzing the
100 ppb tuning solution at the end of each ICP/MS run. The isotopes are
listed in the first column from the left in the Tuning Section of the
Form.
Under "Response Factor, Initial", enter the value for the measured
response factor (in counts per second, to the nearest whole number) in
the 100 ppb tuning solution analyzed at the beginning of each ICP/MS
run, for each mass to charge ratio listed in the first column from the
left in the Response Factor Section of the Form.
Under "Response Factor, Final*, enter the value for the measured
response factor (in counts per second, to the nearest whole number) in
the 100 ppb tuning solution analyzed at the end of each ICP/MS run for
each mass to charge ratio listed in the first column from the left in
the Response Factor Section of the Form.
Under "Observed Mass", enter the observed mass (to nominal unit mass) in
the 100 ppb tuning solution analyzed at the beginning of each ICP/MS run
for each mass to charge ratio listed in the first column from the left
in the Mass Calibration Section of the Form.
The values measured and reported in the Tuning, Response Factor, and
Mass Calibration Sections of the Form must be within the control limits
listed in the second column from the left in each of the Sections.
Note that for every initial solution reported there must be a final one.
However, the opposite is not true. If a tuning solution was required to
be analyzed in the middle of a run (to avoid exceeding the 8-hour
limit), it must be reported in the "Final" section of this form.
B-35 10/91
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If more tuning solutions analyses were required, submit additional Foras
XIV in the order explained in Part D as appropriate.
The order of reporting the tuning solution results oust follow the
teaporal order in which the solutions were run starting with the first
Fora XIV and continuing to the following Fora XIV, as appropriate.
ICP/MS Interna^ gE.«'i
-------
including all QC operations applicable to che SDG (formatted according
Co Table 1, Exhibit B). All EPA sample numbers must be listed in
increasing temporal (date and time) order of analysis, continuing to Che
nexc Form XV for che instrument run if applicable. The analysis date
and time of other analyses not associated with the SDG, but analyzed by
Che instrument in che reported analytical run, must be reported. Those
analyses must be identified with the EPA Sample No. of "ZZZZZZ".
Samples identified as "ZZZZZZ" need not have intensities reported for
internal standards.
Under "Time", enter the time (in military format - HHMM) at which each
analysis was performed.
For any particular ICP/MS run, the EPA Sample No. and time sequence on
Form XV and XVI muse be identical.
Under "Internal Standards %D For:", enter che chemical symbol of the
internal standard in the two-space header field provided to indicate the
internal standard for which che percent differences in that column were
reported.
In Che column, enter the percent relative intensity (to the nearest
whole number) of che intensity of the internal standard in the EPA
Sample Number for each sample analysis listed on the form (excluding
"ZZZZZZ*) and the intensity of che internal standard in the blank
calibration standard (SO). The percent relative intensity (%R) is
calculated using che following formula:
SOI
%R - x 100
SI
Where, che SOI is che intensity of che internal standard in che blank
calibration standard, and SI is the intensity of internal standard in
che EPA Sample No. in Che same units.
Under the "Q" column to the right of each %R column, enter an "E" if the
%R for a field sample, PES, duplicate, or spike is less than 30% or
greater than 125% for the second time after being run at a five-fold
dilution. If the percent relative intensity is greater than 30% and
less than 125%, Chen leave Che field empty.
Columns of internal standard %R must be entered left to right starting
wich the internal sCandards of the lower mass on che first Form XV and
proceeding to che following Form XV as appropriate.
R. Analysis Run Log (A1 [Form ZVI-LCIN]
This form is used Co report the sample analysis run log for ICP and
ICP/MS only. In addition, che samples reported on this form must have
been prepared in che same manner using no pre-preparation dilution or
concentration steps. The results^reporced on Form I for the samples
listed on chis form .fo-r'jaaoh ana^te joust b* .obtained by multiplying
each analyte's concentration (in«ug/L)tfrom the instrument by the
dilution factor listed on the form.
B-37 10/91
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A run is defined as the continuous totality of analyses performed by an
instrument throughout the sequence initiated by, and including, the
initial and the final tuning solution, the first required calibration
standard and terminated by, and including, the continuing calibration
verification and blank following the last required analytical sample.
All field samples and all quality control analyses (including tuning
solutions, ICP serial dilutions, calibration standards, ICVs, CCVs,
ICBs, CCBs, MTS, CRIs, ICSs, LRSs, LCSs, PBs, duplicates, PE samples,
and spikes) associated with the SDG must be reported on Form XVI. The
run must be continuous and inclusive of all analyses performed on the
particular instrument during the run.
Submit one Form XVI per run if no more than 32 analyses, including
instrument calibration, were analyzed in the run. If more than 32
analyses were performed in the run, submit additional Forms XVI as
appropriate.
Complete the header information according to the instructions in Part A,
and as follows.
For "Instrument ID Number", enter the instrument ID number (12 spaces
maximum) which must be an identifier designated by the laboratory to
uniquely identify each instrument used to produce data which are
required to be reported in the SDG deliverable. If more than.one ICP or
ICP/MS instrument is used, submit additional Forms XVI as appropriate.
For "Run No.", enter the run number as explained in Part P.
For "Method", enter the method code (two characters maximum) according
to the specifications in Part C.
For "Start Date", enter the date (formatted MM/DD/YY) on which the
analysis run was started.
For "End Date", enter the date (formatted MM/DD/YY) on which the
analysis run was ended.
Under "EPA Sample No.*, enter the EPA sample number of each analysis,
including all QC operations applicable to the SDG (formatted according
to Table 1, Exhibit B) . All EPA sample numbers must be listed in
increasing temporal (date and time) order of analysis, continuing to the
next Form XVI for the instrument run if applicable. The analysis date
and time of other analyses not associated with the SDG, but analyzed by
the instrument in the reported analytical run, must be reported. Those
analyses must be identified with the EPA Sample No. of "ZZZZZ2".
Under "Prep. Batch Number", enter the preparation batch number for each
sample and quality control sample preparation (including duplicates,
spikes, LCSs, PBs, and PE samples) that are reported on the Form. The
preparation batch number is used to link the sample analysis with the
appropriate preparation batch. It consists of an ordered combination of
the date of preparation (formatted MMDDYY), the hour of preparation (in
military format - HH), and the method of preparation. The preparation
batch number must be left justified and may not have any blank spaces
B-38 10/91
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between its components. It may not have more than one leading blank.
Single digit hours and months must be padded to the left with zeros.
The following are examples of preparation batch numbers:
Prep. Batch Number Preparation
Hour Date Method
"11308915CV" 15 11/30/89 CV
"11038915P " 15 11/30/89 P
-01029008F " 8 01/01/90 F
"12908F " invalid
Under "Time*, enter the time (in military format • HHMM) at which each
analysis was performed.
Note that for a particular sample a dilution factor of "1" must be
entered if the preparation product was analyzed without adding any
further volume of dilutant or any other solutions to the sample or an
aliquot of that sample taken for preparation.
For supplied solutions such as ICVs. ICSs, PESs, and LCSs, a dilution
factor must be entered if the supplied solution had to be diluted to a
dilution different from that specified by the instructions provided with
the solution. The dilution factor reported in such a case must be that:
which would make the reported true values on the appropriate fora for
the solution equal those that were supplied with the solution. For
instance, I CV-2 (0887) has a true value of 104.0 ug/L at a 20 fold
dilution. If the solution is prepared at a 40 fold dilution, a dilution
factor of "2" must be entered on Form XVI and the uncorrected instrument
reading is compared to a true value of 52 ug/L. In this example, Form
II will have a true value of 104.0 regardless of the dilution used. The
found value for the ICV must be corrected for the dilution listed on
Form XVI using the following formula:
Found value on Form II - Instrument readout in ug/L x D/F
Under "Analytes", enter "X" in the column of the designated analyte to
indicate that the analyte value was used from the reported analysis to
report data on any of the forms in the SDG. Leave the column empty for
each analyte if the analysis was not used to report the particular
analyte.
S. Analysis Run Log (Bt [Form XVII-LCIN]
This form is used to report the sample analysis run log for each
instrument used for analysis in the SDG. This includes ICP and ICP/MS
analysis runs where conditions for reporting on Form XVI were not met.
Form XVII is analyte and method specific.
A run is defined as the continuous totality of analyses performed by an
instrument throughout the sequence initiated by, and including, the
B-39 io/91
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initial and the final tuning solution, the first required calibration
standard and terminated by, and including, the continuing calibration
verification and blank following the last required analytical sample.
field samples and all quality control analyses (including tuning
solutions, serial dilutions, calibration standards, ICVs, CCVs, ICBs,
CCBs, MTS, CRIs, ICSs, LRSs, LCSs, PBs, duplicates, PE Samples, matrix
spikes, analytical spikes, and each addition analyzed for MSA
determination) associated with the SDG muse be reported on Form XVII.
The run must be continuous and inclusive of all analyses performed on
the particular instrument during the run.
Submit one Form XVII per run if no more than 32 analyses, including
instrument calibration, were analyzed in the run. If more than 32
analyses were performed in the run, submit additional Forms XVII as
appropriate .
Complete the header information according to the instructions in Part A,
and as follows.
For "Instrument ID Number", enter the instrument ID number (12 spaces
maximum) which must be an identifier designated by the laboratory to
uniquely identify each instrument used to produce data which are
required to be reported in the SDG deliverable. If more than one
instrument is used, submit additional Forms XVII as appropriate.
For "Run No . " , enter the run number as explained in Part P .
For "Method" , enter the method code ( two characters maximum) according
to the specifications in Part C.
For "Start Date", enter the date (formatted MM/DD/YY) on which the
analysis run was started.
For "Analyte", enter the analyte's chemical symbol (three spaces
maximum) for which the analysis run is being reported on the Form.
Submit a Form XVII for each analyte analyzed.
For "End Date", enter the date (formatted MM/DD/YY) on which the
analysis run was ended.
For "Retention Tine Window", enter the retention time window (in
seconds, to two decimal places) established for the column used for
analysis of the analyte on this form if the method used is "1C".
For the "Lower Limit", enter the retention time lower limit (in seconds,
to two decimal places) for the ion chroma tography (1C) column used for
analysis on this form.
For the "Upper Limit", enter the retention time upper limit (in seconds,
to two decimal places) for the Ion Chromatography (1C) column used for
analysis on this, fojmk, '* ,' ; .' '
B-40 10/91
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Note that the difference between the "Upper Limit" and "Lower Limit" of
the retention time must equal the "Retention Time Window". If the
method reported on this form is not "1C", leave the "Retention Time
Window", "Lower Limit", and "Upper Limit" fields blank.
Under "EPA Sample No.", enter the EPA sample number of each analysis,
including all QC operations applicable to the SDG (formatted according
to Table 1, Exhibit B). All EPA sample numbers must be listed in
increasing temporal (date and time) order of analysis, continuing to the
next Form XVII for the instrument run if applicable. The analysis date
and time of other analyses not associated with the SDG, but analyzed by
the instrument in the reported analytical run, must be reported. Those
analyses must be identified with the EPA Sample No. of "ZZZZZZ".
Under "Prep. Batch Number", enter the preparation batch number as
explained in Part R.
Under "Inl. Vol.", enter the initial volume (in mL, to the nearest whole
number) of each sample or aliquot of the sample taken for preparation
(distillation, digestion, etc.) for analysis by the method indicated in
the header section of the Form. This field must have a value for each
field sample listed.
Under "Fin. Vol.", enter the final volume (in mL, to the nearest whole
number) of the preparation for each sample prepared for analysis by the
method indicated in the header section of the Form. This field must
have a value for each field sample listed.
Under "Time", enter the time (in military format - HHMM) at which each
analysis was performed.
Under "D/F", enter the dilution factor (to two decimal places) by which
the final product of preparation procedure (digestate or distillate)
needed to be diluted for each analysis performed.
Note that for a particular sample, a dilution factor of "1* must be
entered if the preparation product was analyzed without adding any
further volume of dilutant or any other solution to the "Fin. Vol." of
Che sample or an aliquot of that "Fin. Vol." listed for that sample on
this form.
For supplied solutions such as ICVs, ICSs, and LCSs, a dilution factor
must be entered if the supplied solution had to be diluted to a dilution
different from that specified by the instructions provided with the
solution. The dilution factor reported in such a case must be that
which would make the reported true values on the appropriate form for
the solution equal those that were supplied with the solution. For
instance, ICV-2(0887) has a true value of 104.0 ug/L at a 20 fold
dilution. If the solution is prepared at a 40 fold dilution, a dilution
factor of "2" must be entered on Form XVII and the uncorrected
instrument reading is compared to a true value of 52 ug/L. In this
example, Form II will have a true value of 104.0 regardless of the
dilution used. The found value for the ICV must be corrected for the
dilution listed on Form XVII using the following formula:
B-41 10/91
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Found value on Form II - Instrument readout in ug/L x D/F
Under "%R", enter the percent recovery (to two decimal places) for each
analytical spike analyzed. Leave the field blank if the analysis
reported is not an analytical spike. A %R of "-9999" must be entered
for the analytical spike if either the sample or the analytical spike
result is greater than the calibration range of the instrument.
Under "%RSD", enter the relative standard deviation of the replicate
exposures or injections for each analysis reported on this form.
Under "Retention Time", enter the retention time (in seconds, to two
decimal places) for each analysis reported on this form. The retention
time must be within the lower and upper limits reported on the Form.
Leave the field blank If the method reported on Che form is not "1C*.
Standard Solutions Sources [Form ZVIII-LCIH]
This form is used to report the source of each standard solution on an
analyte--by-analyte basis used for initial and continuing calibration
verifications, CRDL, LRS, ICS, and LCS standards used as a QC analysis
in the SDG.
Complete the header information according to the instructions in Part A,
and as follows.
Under "ICV Standard Source", enter the initial calibration source (10
spaces maximum) for each analyse for which ICV results were reported on
Form II. For supplied solutions, entering "SMC* is not sufficient.
Supplied solutions must be identified using the codes supplied with the
solutions for identification. For solutions that are not provided,
enter sufficient information in the available 12 spaces to unequivocally
identify the manufacturer and the solution used.
Under "CCV Standard Source", enter the continuing calibration source (10
spaces maximum) for each analyte for which CCV results were reported on
Fora II, as described for the initial calibration source.
Under "CRI Standard Source", enter the CRDL standard source (10 spaces
maximum) for each analyte for which CRDL standard results were reported
on Form III, as described for the initial calibration source.
Under "LRS Standard Source", enter the Linear Range Analysis source (10
spaces maximum) for each analyte for which LRS standard results were
reported on Form IV, as described for the initial calibration source.
Under "ICS Standard Source", enter the ICP and ICP/MS Interference
source (10 spaces maximum) for each analyte for which ICS standard
results were reported on Form VI, as described for the initial
calibration source.
Under "LCS Standard Source", enter the Laboratory Control Sample source
(10 spaces maximum) for each analyte for which LCS standard results were
reported on Form IX, as described for the initial calibration source.
B-42 10/91
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U. Sample Log-In Sheet [Form DC-1]
This form is used Co document the receipt and inspection of samples and
containers. One original of Form DC-1 is required for each sample
shipping container, e.g., cooler. If the samples in a single sample
shipping container oust be assigned to more than one Sample Delivery
Group, the original Form DC-1 shall be placed with the deliverables for
the Sample Delivery Group of the lowest Arabic number and a copy of Form
DC-1 trust be placed with the deliverables for the other Sample Delivery
Group(.«->M The copies should be identified as "copy(ies) , * and the
locatioi ; '• the original should be noted on the copies.
Sign and dace Oie airbill (if present). Examine the shipping container
and record the presence/absence of custody seals and their condition
(i.e., intact, broken) in item 1 on Form DC-1. Record the custody seal
numbers in item 2.
Open the container, remove the enclosed sample documentation, and record
the presence/absence of chain-of-custody record(s), SMO forms (i.e.,
Traffic Reports, Packing Lists), and airbills or airbill stickers in
items 3-5 on Form DC-1. Specify if there is an airbill present or an
airbill sticker in item 5 on Form DC-1. Record the airbill or sticker
number in item 6.
Remove the samples from the shipping container(s), examine the samples
and the sample tags (if present), and record the condition of the sample
bottles (i.e., intact, broken, leaking) and presence or absence of
sample tags in items 7 and 8 on Form DC-1.
Review the sample shipping documents and complete the header information
described in Part A. Compare the information recorded on all the
documents and samples and mark the appropriate answer in item 9 on Form
DC-1.
If there are no problems observed during receipt, sign and date (include
time) Form DC-1, the chain-of-custody record, and Traffic Report, and
write the sample numbers on Form DC-1. Record the appropriate sample
tags and assigned laboratory numbers if applicable. The log-in date
should be recorded at the top of Form DC-1 and the date and time of
cooler receipt at the laboratory should be recorded in items 10 and 11.
Cross out unused columns and spaces.
If there are problems observed during receipt, contact SMO and document
the contact as well as resolution of the problem on a CLP Communication
Log. Following resolution, sign and date the forms as specified in the
preceding paragraph and note, where appropriate, the resolution of the
problem.
Record the fraction designation (if appropriate) and the specific area
designation (e.g., refrigerator number) in the sample transfer block
located in the bottom left corner of Form DC-1. Sign and date the
sample transfer block.
B-43 10/91
-------
V. Document Inventory Sheet (Form DC-2)
This fora is used to record the inventory of the Complete SDG File (CSF)
documents which are sent to the Region.
Organize all CSF documents as described in Exhibit B, Section II and
Section III. Assemble the documents in the order specified on Form DC-2
and Section II and III, and stamp each page with the consecutive number.
(Do not number the DC-2 form). Inventory the CSF by reviewing the
document numbers and recording page numbers ranges in the column
provided on the Form DC-2. If there are no documents for a specific
document type, enter an "NA" in the empty space.
Certain laboratory-specific documents related to the CSF may not fit
into a clearly defined category. The laboratory should review Form DC-2
to determine if it is most appropriate to place them under No. 29, 30,
31, or 32. Category 32 should be used if there is no appropriate
previous category. These types of documents should be described or
listed in the blanks under each appropriate category.
B-44 10/91
-------
SECTION IV
DATA REPORTING FORKS
B-45 10/91
-------
-------
LOW CONCENTRATION INORGANICS
COVER PAGE
Lab Name:
Lab Code:
SOW No.:
Contract::
Case No.:
EPA Sample No.
SAS No.:
SDG No.
Lab Sample ID.
Were ICP and ICP/MS interelement corrections applied? (Yes/No)
Were ICP and ICP/MS background corrections applied? (Yes/No)
If yes, were raw data generated before
application of background corrections? (Yes/No)
Comments:
ICP ICP/MS
I certify that this data package is in compliance with the terms and
conditions of the contract, both technically and for completeness, for
other than the conditions detailed above. Release of the data contained
in this hardcopy data package and in the computer-readable data submitted
on diskette has been authorized by the Laboratory Manager or the
Manager's designee, as verified by the following signature.
Signature:
Date:
COVER PAGE
Name:
Title:
- LCIN
10/91
-------
Lab Name:
Lab Code:
LOW CONCENTRATION INORGANICS
ANALYSIS DATA SHEET
EPA SAMPLE NO.
Contract:
Case No.:
SAS No.:
SDG No.
Lab Sample ID:
Date Received:
Before:
After:
Concentration Units: ug/L
CAS No.
7429-90-5
74'40-36-Q
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-3
744O-70-2
7440-48-4
7440-50-8
7439-89-6
7439-92-1
7439-95-4
7439-96-5
7439-97-6
7440-02-7
7440-02-0
7882-49-2
7440-22-4
7440-23-5
7440-28-0
7440-62-2
7440-66-6
1698-44-88
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Potassium
Nickel
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Fluoride
NO2/NO3-N
Concentration
C
Q
M
Color
Clarity
Viscosity
Comments:
FORM I
- LCIN
10/91
-------
f LOW CONCENTRATION INORGANICS
INITIAL AND CONTINUING CALIBRATION VERIFICATION
Lab Name:
Lab Code:
Run No.:
Contract:
Case No.:
SAS No.:
SDG No.:
Concentration Units: ug/L
\iialyte
Aluminum_
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium_
Vanadium_
Zinc
Cyanide
Fluoride
NO2/NO3-N
w
O
M
N
—
—
—
—
—
—
Initial Calibration
True Found %R
Continuing Calibration
True Found %R Found %R
1122
M
Comments:
FORM II
- LCIN
10/91
-------
LOW CONCENTRATION INORGANICS
CRDL STANDARDS
Lab Name:
Lab Code:
Run No.:
Contract:
Case No.:
SAS No.:
SDG No.
Comments:
Concentration Units: ug/L
Analyte
Aluminum
Antimony_
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Fluoride
NO2/NO3-N
W
O
M
N
True
Initial
Found
%R
Final
Found
%R
M
FORM III
- LCIN
10/91
-------
LOW CONCEMT.ATION INORGANICS
1*.
LRS
Lab Name:
Lab Code:
Run No.:
Contract:
Case No.:
SAS No.:
SDG No.
Concentration Units: ug/L
Analyte
Aluminum
Antimony
Arsenic
Bariua
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Fluoride
NO2/N03-N
W
0
M
N
I
True
nitial
Found
*R
Final
Found
%R
M
Comments:
FORM IV
- LCIN
10/91
-------
LOW CONCENTRATION INORGANICS
BLANKS
Lab Mane:
Lab Code:
Run No.: .
Case No.:
Contract:
SAS No.
SDG No.
Concentration Units: ug/L
Analyte
Aluminum.
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Coooer
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium_
Vanadium
Zinc
Cyanide
Fluoride
N02/N03-N
W
o
M
N
~~
-
-
^^
-
Initial
Calib.
Blank C
-
-
•»
-
—
-
—
Continuing calibration Blanks
1 C 2 C 3 C
-
—
-
—
—
^^
-
—
_
-
-
—
—
-
—
Prep.
Blank
C
M
Comments:
FORM V
- LCIN
10/9.
-------
LOW CONCENTRATION INORGANICS
f
ICS
Lab Name:
Lab Code:
Contract:
Case No.:
SAS No.:
SDG No.:
Instrument ID Number:
Run No.:
Concentration Units: ug/L
Analyte
Aluminum_
Antimony""
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt ~
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
w
0
M
N
—
-
-
—
True
Sol . Sol .
A AB
Initial Found
Sol . Sol .
A AB %R
Final Found
Sol. Sol.
A AB %R
M
Comments:
FORM VI
- LCIN
10/9'
-------
LOW CONCENTRATION INORGANICS
SPIKE SAMPLE RECOVERY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.
SOG No.
Concentration Units: ug/L
Analyte
Aluminum
Antinony_
Arsenic
Barium
Beryllium
r>3"fr"iiimB
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Nickel
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Fluoride
N02/N03-N
W
0
M
N
Control
Limit
%R
Sample
Result (SR)
C
Spiked Sample
Result (SSR)
C
_
Spike
Added (SA)
%R
Q
^•k
M
Comments:
10/91
FORM VII
- LCIN
-------
Lab Name:
Lab Code:
LOW CONCENTRATION INORGANICS
DUPLICATES
Contract:
EPA SAMPLE NO.
Case No.
SAS No.:
SDG No.
Concentration Units: ug/L
Comments:
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Fluoride
NO2/NO3-N
w
o
M
N
_
Control
Limit
Sample (S)
c
_
Duplicate (D)
c
RPD
Q
M
FORM VIII
- LCIN
10/91
-------
LOW CONCENTRATION INORGANICS
LCS
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.
SDG No.
Concentration Units: ug/L
Analyte
Aluminum
Antimony_
Arsenic ""
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt ~"
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Fluoride
NO2/NO3-N
W
O
M
N
—
—
—
—
-
—
._
Limits
Lower Upper
•
True Found
c
-
-
—
—
-
-
—
%R
M
Comments:
FORM IX
- LCIN
10/91
10
-------
Lab Name:
Lab Code:
LOW CONCENTRATION INORGANICS
C
SERIAL DILUTION
Contract:
Case No.:
SAS No.:
EPA SAMPLE NO.
SDG NO.
Concentration Units: ug/L
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Fluoride
NO2/N03-N
W
O
M
N
_
Initial Sample
Result (I)
C
Serial Dilution
Result (S)
C
%
Difference
Q
M
Comments:
FORM X
- LCIN
10/91
11
-------
LOW CONCENTRATION INORGANICS
STANDARD ADDITION RESULTS
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.
SDG No.
Concentration Units: ug/L
EPA
Sanple
No.
An
Zero
Found
A D 1
First
Added
Found
3 I T I O N S
Second
Added
Found
Third
Added
Found
Final
Cone.
r
Q
-
-
—
—
—
—
-
M
FORM XI
- LCIN
10/91
12
-------
LOW CONCENTRATION INORGANICS
*•
IDL
Lab Name:
Lab Code:
Case No.:
Instrument ID Number:
Contract: _
SAS NO.
Method:
SDG No.:
Date:
Concentration Units: ug/L
Analyte
Aluminum
Antimony_
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Fluoride
N02/NO3-N
Wavelength
or
Mass
Number
(WOMN)
Wave-
Length
(nm)
Mass
(m/z)
Integ.
Time
(sec)
Back-
ground
CRDL
100
5
2
20
1
1
500
10
10
10
100
2
500
10
0.2
20
750
3
10
500
10
10
20
10
200
100
IDL
Comments:
FORM XII
- LCIN
10/91
13
-------
LOW CONCENTRATION INORGANICS
lUTERELEMENT CORRECTION FACTORS
Lab Name:
Lab Code:
Case No.:
Instrument ID Number:
Contract: __
SAS No.
Method:
SOG No.
Date:
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Wave-
Length
or
Mass
Ini
berelement <
Correction J
factors fc
ar:
Comments:
FORM XIII
- LCIN
10/91
-------
LOW CONCENTRATION INORGANICS
ICP/MS TUNING AND RESPONSE FACTOR CRITERIA
Lab Name:
Lot Code:
Instrument ID Number:
Analysis Date:
Contract :
Case No. : SAS No. :
Run No. :
Analysis Times: (initial)
SD6 No.:
Method:
(Final)
Tuning
BJ/Z
7Li/59Co
59CO/59CO
115In/59CO
205T1/59CO
Ion
Abundance
Criteria
(0.20 - 1.00)
( 1.00 )
(0.75 - 2.00)
(0.50 - 1.20)
% Relative
Initial
Abundance
Final
Response Factor (counts per second)
m/2
7Li
59CO
llSIn
102RU
205T1
Response
Factor
Criteria
( > 2.000 )
( >20.000 )
( >10.000 )
( < 25 )
( > 1.000 )
RF100 (1)
Initial
Response
Final
(1) Background (RFO) for l02Ru
Mass Calibration
m/z
7Li
59Co
H5In
205T1
Acceptable
Mass Range
( 6.9160 - 7.1160)
( 58.8332 - 59.0332)
(114.8040 - 115.0040)
(204.8744 - 2O5.0744)
Observed Mass
FORM
- LCIN
10/91
15
-------
LOW CONCENTRATION INORGANICS
ICP/MS INTERNAL STANDARDS SUMMARY
Lab Name:
Lab Code:
Instrument
Start Date
EPA
Sample
No.
ID Number:
•
•
Time
Case Nc
—
). :
Q
C<
i
Internal
—
sn1
. S
Q
:ract :
SAS No. :
Run No. :
Standards
—
%!
Q
_
SDC
Me
End
I For:
—
; »
itt
Da
Q
ro.:
LOd:
ite:
—
Q
FORM XV
- LCIN
10/91
16
-------
LOW CONCENTRATION INORGANIC
ANALYSIS RUN LOG (A) "
Lab Name:
Lab Code:
Instrument
Start Date
EPA
Sample
No.
ID Number:
*
Prep.
Batch
Number
Ca
Time
se No. :
D/F
A
L
S
B
A
S
C
B
A
ton
B
E
iti
S
R
C
D
•ac
AS
mi
C
A
;t
t
h
C
R
»
»
Jo.
to.
C
o
•
•
•
*
A]
C
D
na
F
E
iy
p
B
te
M
6
S
M
N
£
En
H
6
IDG
Me
d
N
I
; h
!th
Da
K
Fo.
LOG
te
S
E
•
1:
•
A
G
N
A
T
L
V
Z
N
FORM XVI
- LCIN
10/91
17
-------
LOW CONCENTRATION INORGANICS
ANALYSIS RUN LOG (B)
Lab Name:
Lab Code:
Instrument
start Date
ID Number:
Case
No.:
Contract:
SAS No.:
Run No. :
: Analyte:
Retention Time Window
EPA
Sample
Mo.
Prep.
Batch
Number
: Lower Limit:
Inl.
Vol.
Fin.
Vol.
Time
t
D/F
%R
SDG No. :
Method:
End Da1
Jpper Limj
%RSD
:e:
it:
Retention
Time
FORM XVII
- LCIN
10/91
18
-------
SAMPLE LOG-IN SHEET
labNam*
Pan. C
-------
LOW COHCEmUIXXaM WATER JFOK INORGANIC AHALXTES
COMPLETE SDO FILE (CSF)
Lab Name; City/State:
Case No. SDG No. SOG Noa. to Follow:
SAS Mo. Contract No. SOW No.
All documanta deliver ad in the Complete SDG File muat be original documents
where possible. (Reference Exhibit B, Section II D and Section III V)
Pane Noa. (Please Check:)
From To Lab Region
1. Inventory Sheet (DC-2) (Do not number)
2. Cover Page
3. Inorganic Analysis Data Sheet (Form I)
4. Initial £ Continuing Calibration ^_^
Verification (Form II - LCIN)
5. CRDL Standards (Form III - LCIN)
6. Linear Range Standarda (Form IV-LCIN)
7. Blanks (Form V-LCIN) -
8. ICP & ICP/MS Interference Check
Sample (Form VI-LCIN)
9. Spike Sample Recovery (Form VII-LCIN)
10. Duplicates (Form VIll-LCIN)
11. Lab Control Sample (Form IX-LCIN)
12. Serial Dilution (Form X-LCIN)
13. Standard Addition Results
(Form XI-LCIN)
14. Instrument Detection Limits
(Form XII-LCIN)
15. Interalement Correction Factor
(Form XIII-LCIN)
16. ICP/MS Tuning fi Response Factor
Criteria (Form XIV-LCIN)
17. ICP/MS Internal Standards Summary
(Form XV-LCIN)
18. Analysis Run Log (A) (Form XVI-LCIN)
19. Analysis Run Log (B) (Form XVII-LCIN)
20. Standard Solutions Sources
(Form XVIII-LCIN)
21. ICP Raw Data
22. ICP/MS Raw Data
23. HYICP Raw Data
24. Furnace AA Raw Data
Form DC-2 4/90
-------
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
Pace Nos.
From To
(Please Check:)
Lab Region
Mercury Raw Data
Cyanide Raw Data
Fluoride Raw Data
Total Nitrogen Raw Data
Preparation Logs
Traffic Report
EPA Shipping/Receiving Documents
Airbill (No. of Shipments )
Chain—of-Cu«tody Records
Sample Tags
Sample Log-In .Sheet (Lab & DC1)
SDG Cover Sheet
Misc. Shipping/Receiving Records
(list all individual records)
Telephone Logs
Internal Lab Sample Transfer Records £
Tracking Sheets (describe or list)
Internal Original Sample Prep & Analysis Records
(describe or list)
Prep Records
Analysis Records
Description
Other Records (describe or list)
Telephone Communication Log
36. Comments:
Completed by (CLP Lab):
(Signature)
Audited by (EPA):
(Print Name & Title)
(Date)
(Signature) (Print Name & Title) (Date)
Form DC-2 (continued) 4/90
-------
EXHIBIT C
TABLES
PAGE
TABLE I: INORGANIC TARGET ANALYTE LISV ''AL) C'1
TABLE II: INORGANIC TARGET ANALYTE LIST (TA^,) FOR ICP/MS ANALYSES C-3
TABLE III: ICV, CCV, CRDL, AND LCS STANDARD
CONTROL LIMITS FOR INORGANIC ANALYSES C-4
TABLE IV: SPIKING LEVELS FOR MATRIX SPIKE c'5
TABLE V: INTERFERENCE CHECK SAMPLE COMPONENTS AND
CONCENTRATIONS FOR ICP AND ICP/MS c'6
TABLE VI: EXAMPLE OF ANALYTE CONCENTRATION EQUIVALENTS («g/L)
ARISING FROM INTERFERENCES AT THE 100 mg/L LEVEL
FOR ICP/OES c-7
TABLE VII: TUNING SOLUTION FOR ICP/MS C-8
TABLE VIII: TUNING, RESPONSE FACTOR AND MASS CALIBRATION
CRITERIA FOR ICP/MS C-9
TABLE IX: MEMORY TEST SOLUTION FOR ICP/MS C-10
TABLE Z: INTERNAL STANDARDS THAT MAY BE USED IN ICP/MS C-ll
TABLE XI: RECOMMENDED ELEMENTAL EXPRESSIONS FOR ISOBARIC
INTERFERENCES FOR ICP/MS C-12
TABLE XII: CONTRIBUTIONS OF CONCOMITANT ELEMENTS TO NEARBY
ANALYTES FOR ICP/MS WHEN RESOLUTION AIH) MEASUREMENT
SCHEMES VARY C'13
TABLE XIII: ISOBARIC MOLECULAR-ION INTERFERENCES THAT COULD AFFECT
THE ANALYTES C-14
TABLE XIV: MASS CHOICES FOR ELEMENTS WHICH MUST BE MONITORED
EITHER DURING THE ANALYTICAL RUN OR IN A SEPARATE
SCAN FOR ICP/MS C-16
10/91
-------
TABLE I
INORGANIC TARGET ANALYTE LIST (TAL)
Contract Required
Detection Linit
(1.2)
Analyte (ug/L)
Aluminum 100
Antimony 5
Arsenic 2
Bariua 20
Beryllium 1
Cadniun 1
Calciua 500
Chromium 10
Cobalt 10
Copper 10
Iron 100
Lead . 2
MagnesiuB 500
Manganese 10
Mercury 0.2
Nickel 20
Potassium 750
Selenium 3
Silver 10
Sodium 500
Thallium 10
Vanadium 10
Zinc 20
Cyanide 10
Fluoride 200
N02/NO3-N 100
(1) Any analytical method specified in Exhibit D may be utilized-, except
for the ICP/MS method (see Table II) and the 1C method for Fluoride,
provided the documented instrument detection limits meet the Contract
Required Detection Limit (CRDL) requirements. Higher detection limits may
only be used in the following circumstance:
C-l 10/91
-------
If Che sample concentration exceeds five tines the detection limit of the
instrument or method in use, the value nay be reported even though the
instrument detection limit may not equal the Contract Required Detection
Limit. This is illustrated in the example below:
For lead:
Method in use - 1CP
Instrument Detection Limit (IDL) - 40
Sample concentration - 220
Contract Required Detection Limit (CRDL) - 2
The value of 220 may be reported even though instrument
detection limit is greater than CRDL. The instrument
detection limit must be documented as described in Exhibit
E.
(2) The CRDL is the instrument detection limits obtained in pure water that
must be met using the. procedure in Exhibit E. The detection limits for
samples may ue considerably higher depending on the sample matrix.
C-2 10/91
-------
TABLE II
INORGANIC TARGET ANALYTE LIST (TAL)
FOR ICP/MS ANALYSES
Contract Required
Detection Linit
(1,2)
Analyte ~ (ug/L)
Aluminum 100
Antimony 5
Arsenic 2
Barium 20
Beryllium 1
Cadmium 1
Chromium 10
Cobalt 10
Copper 10
Iron 100
Lead 2
Manganese 10
Nickel 20
Selenium 3
Silver 10
Thallium 10
Vanadium 10
Zinc 20
(1) The ICP/MS method specified in Exhibit D may be utilized provided the
documented instrument detection limits meet the Contract Required Detection
Limit (CRDL) requirements.
(2) The CRDL is the instrument detection limits obtained in pure water that
must be met using the procedure in Exhibit E. The detection limits for
samples may be considerably higher depending on the sample matrix.
C-3 10/91
-------
TABLE III
INITIAL AND CONTINUING CALIBRATION VERIFICATION.
CRDL STANDARD CONTROL LIMITS, AND LCS STANDARD CONTROL LIMITS
FOR INORGANIC ANALYSES
INITIAL
Analytical Method
ICP/AA
ICP/MS
ICP/HYDRIDE.
Cold Vapor AA
Other
Other
Other
AND CONTINUING CALIBRATION
Inorganic Species
Metals
Metals
Metals
Mercury
Cyanide
Fluoride
NOo/NOvN
VERIFICATION LIMITS
% of True Value (EPA Set)
Low Limit
90
90
90
80
85
85
90
High Limit
110
110
110
120
115
115
110
CRDL STANDARD CONTROL LIMITS
% of True Value tEPA Set)
Analytical Method
ICP/OES and AA
ICP/MS
ICP/HYDRIDE
Cold Vapor AA
Other
Other
Other
Inorganic Species
Metals
Metals
Metals
Mercury
Cyanide
Fluoride
N02/NO3-N
Low Limit
50
50
50
50
50
50
50
High Limit
150
150
150
150
150
150
150
LCS STANDARD CONTROL LIMITS
The LCS Standard Control Limits are the same for all inorganic species. The
limits are 80 - 120.
C-4
10/91
-------
TABLE IV
SPIKING LEVELS FOR MATRIX SPIKE(1)
Elemei\g Water (ug/L)
Aluminum 509->>
Antimony 50 &'
Arsenic 10(3J
»/.«.-: m 200
Bc*y; r\iuin 10
Cadmivjua 10
Calcium *
ChroaiuB SO
Cobalt 100
Copper 50
Iron 250
Lead 25
Magnesium *
Manganese 50
Nickel 100
Potassiun *
Selenium 5
Silver 50
Sodium *
Thallium 50
Vanadium 100
Zinc 100
Mercury 0.5
Cyanide 100
Fluoride 400
200
(1) The levels shown indicate concentrations added in the final digestate
of the spiked sample.
(2) The spike must be made with a solution containing antimony in the +5
oxidation state.
(3) The spike must be made with a solution containing arsenic in the +5
oxidation state.
(4) The spike must be made with a solution containing selenium in the +6
oxidation state.
*No spike required.
C-5 10/91
-------
TABU V
INTERFERENCE CHECK SAMPLE COMPONENTS AND CONCENTRATIONS
FOR ICP AND ICP/MS
Interference Solution A Solution AB
Component Concentration (my/D Concentration fmy/L)
Al 100.0 100.0
Ca 100.0 100.0
Fe 100.0 100.0
Mg 100.0 100.0
Na 100.0 100.0
P 100.0 100.0
K 100.0 100.0
S 100.0 100.0
C 200.0 200.0
Cl 720.0 720.0
Mo 10.0 10.0
Ti 10.0 10.0
As 0.0 0.100
Cd 0.0 0.050
Cr 0.0 0.100
Co 0.0 0.200
Cu 0.0 0.100
Mn 0.0 0.100
Ni 0.0 0.200
Se 0.0 0.100
Ag 0.0 0.100
V 0.0 0.200
Zn 0.0 0.100
NOTE: See Exhibit D, Part E, for additional information.
C-6 10/91
-------
TABLE VI
EXAMPLE OF ANALYTE CONCENTRATION EQUIVALENTS (mg/L)
ARISING FROM INTERFERENTS AT THE 100 mg/L LEVEL FOR 1CP/OES
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Selenium
Silicon
Sodium
Thallium
Vanadium
Zinc
Wavelength
(nm)
308.215
206.833
193.696
455.403
313.042
249.773
226,502
317.933
267.716
228.616
324.754
259.940
220.353
279.079
257.610
202.030
231.604
196.026
288.158
588.995
190.864
292.402
213.856
Al
0.47
1.3
0.04
--
--
--
--
--
--
0.17
•
0.005
0.05
0.23
--
--
0.30
--
"
Interferent
Ca Cr Cu Fe Mg
2.9
0.44
..
0.08 --
..
0.03 --
-.
..
..
0.02 0.11
0.01
--
.-
0.07
..
..
0.05
0.14
0.08
0.32
0.03
0.01 0.01
0.003 --
0.005
0.003 --
..
A
0.13
0.002 0.002
0.03
. * * *
0.09
- -
- - _ .
0.005
" " * -
Mn Ni
0.21
0.02
0.04
0.04
0.03
..
0.12
. _
0.25
- -
-.
• • . _
- - - -
- -
- .
• — • «
- - - -
0.29
';li
.25
0.04
0.03
..
0.15
0.05
, .
. .
0.07
_ _
0.08
..
0.02
V
'..4
v .45
1. '
0.05
0.03
0.04
0.02
0.12
- -
— —
w m
0.01
..
C-7
10/91
-------
TABLE VII
TUNING SOLUTION FOR ICP/MS
The tuning solution oust consist of the following
elements at the stated concentrations.
Concentration
Element
7Li 100
Co 100
In 100
Tl 100
C-8 10/91
-------
TABLE VIII
TUNING. RESPONSE FACTOR AND MASS CALIBRATION CRITERIA
FOR ICP/MS
TUNING CRITERIA
n/2 Ion Abundance Criteria
7Li/59Co ( 0.20 - 1.00 )
59Co/59Co ( 1.00 )
115In/59Co ( 0.75 - 2.00 )
205Tl/59Co ( 0.50 - 1.20 )
RESPONSE FACTOR CRITERIA
Response Factor Criteria
7L1 ( >2.000 )
59Co ( >20,000 >
115 In ( >10,000 )
102Ru ( <25 )
205T1 ( > 1,000 )
HASS CALIBRATION CRITERIA
n>/2 Exact Kass
7Li ( 6.9160 - 7.1160 )
59Co ( 58.8332 - 59.0332 )
H5In ( 114.8040 - 115.0040 )
205T1 ( 204.8744 - 205.0744 )
C-9 10/91
-------
TABLE ix
MEMORY TEST SOLUTION FOR ICP/MS
The memory solution must consist of the following elements:
Element Concentration, (mg/L)
Al 100
Ca 100
Fe 100
Kg 100
Na 100
K 100
C 200
Cl 720 .
Mo 10
P 100
S 100
Ti 10
Sb 10
As 10
Ba 10
Be 10
Cd 10
Cr 10
Co 10
Cu 10
Pb 10
Mn 10
Hi . 10
Se 10
Ag 10
T 10
V 10
Zn 10
*Note: See Exhibit D Part E and Exhibit E for further references to the
sry test solution.
C-10 10/91
-------
TABLE X
INTERNAL STANDARDS THAT MAY BE USED IN ICP/MS
Internal
Standard
Sc
Y
Rh
In
Tb
Ho
-------
TABLE XI
RECOMMENDED ELEMENTAL EXPRESSIONS FOR ISOBARIC INTERFERENCES
FOR ICP/MS
Element
Al
Sb
As
Ba
Be
Cd
Ca
Cr
Co
Cu
Fe
Pb
Mg
Mn
Ni
Ag
Tl
V
Zn
6U
Sc
Y
Rh
In
Tb
Ho
Bi
Se
-
Isobaric
Correction
none
none
ArCl, Se
none
none
MoO, Sn
none
none
none
none
none
none
none
none
none
none
none
CIO, Cr
none
Li (natural)
none
none
none
Sn
none
none
none
Ar2
M - the total
Expression Proportional to Elemental
(1.0000)(27M)
(1.0000)(121M)
(1. 0000) (75M)- (3. 1278) (77M)+(1. 0177) (
(1.0000)(135M)
(1.0000)(9M)
Concentration
78M)
(1. 0000) (114M)-(0. 0268) (118M)-(1. 6285) (108M)
(1.0000)(4AM)
(1.0000)(52M)
(1.0000)(59M)
(1.0000)(65M)
(1.0000)(57M)
(1. 0000) (208M)-K1. 0000) (207M)+(1. 0000) (206M)
(1.0000)(25M)
(1.0000)(55M)
(1.0000)(60M)
(1.0000)(107M)
(1.0000)(205M)
(1 . 0000) (51H) - (3 . 1081) (53M)+(0 . 3524) (
(1.0000)(66M)
(1. 0000) (6M)-(0. 0813) (7M)
(1.0000)(45M)
(1.0000)<89M)
(1.0000)(103M)
(1.0000)(115M)-(0.0149)(118M)
(1.0000)(159M)
(1.0000)(165M)
(1.0000)(209M)
(1. 0000) (78M)-(0. 1869) (76M)
ion count rate at the specified mass.
52M)
C-12
10/91
-------
TABLE XII
CONTRIBUTIONS OF CONCOMITANT ELEMENTS TO NEARBY ANALYTES FOR ICP/KS
WHEN RESOLUTION AND MEASUREMENT SCHEMES VARY
Concentrations listed are the approxinate level (mg/L) of
interferenc that gives an analyte concentration of 10 ug/L.
Peak Width at 10% of the Peak Height
Analte
121
Sb
75
*
U4,
Cd
52
53
59
«
es;
Cr
Cr
Co
Cu
Cu
55
58
Mn
66
Zn
Interferent
Element
120
Sn
>• 7's'
115
In
51V
54Fe
*!Ni. -°Ni
"Ni,
64Zn
!*N
59,
54Fe,
'ft..
63
Cu
108
108
Pd
^cd! -
65Cu, 63Cu
65Cu
1 0 amu
Integration Width
0,9
820
77
910
1,200
1,700
>5,000
30
1.4
650
>1,500
190
4,000
1
>4,400
140
900
>3,000
9
>8 . 500
>2,400
130
1,800
1,600
>2 , 100
>7,800
2
anu 0.3 anu
5
none
4
12
8
150
none
1.5
7
6
1
14
1
22
14
8
96
4
690
22
3
12
10
45
57
none
0.8
ami
Integration Width
0.9 anu
10
1
3
9
10
180
5
none
1
2
none
9
none
15
57
4
75
10
4,500
80
5
36
37
410
410
3
0.3 amu
1
none
none
1
none
18
none
none
none
none
none
none
none
none
none
none
7
5
16
4
2
3
3
1
2
2
C-13
10/91
-------
TABLE XIII
ISOBARIC MOLECULAR-ION INTERFERENCES THAT COULD
AFFECT THE ANALYTES
Oxygen Hydroxyl
Analvte Inter. Inter.
Nitrogen Chlorine Sulfur Carbon
Inter. Inter. Insej^. Inter. Other
l«sb
75Sb
^•3<*Ba
Ba
^•3^Ba
Ba
134^
*• 2Ba
Ba
&
•Li Cd
H2Cd
*^cd
*^Cd
Cd
^•^Cd
^fcd
108Cd
"Cr
«cr
Cr
54Cr
fi?Co
63Cu
5U
PdO
AgO
CoO
SnO
SbO
SnO
SnO
.SnO
SnO,
CdO
MoO
MoO,
MoO
MoO,
MoO
MoO
ZrO
MoO.
ArO
CIO
SO
CaO
TiO,
TiO
NiOH
SbOH
SnOH
SnOH
SnOH
SnOH
CdO InOH
CdOH
MoOH
ZrO MoOH
MoOH
ZrO
MoOH
ZrO ZrOH
C10H
ArOH
C10H
CaOH
P02 TiOH
TiOH
AgN
AgN
NiN
SnN
SnN
SnN, CdN
MoN
MoN
MoN
MoN, ZrN
MoN, ZrN
MoN, ZrN
KN
ArN
ArN, CaN
ScN
TiN
VN
SrCl
ArCl
MoCl
MoCl
MoCl
MoCl
MoCl
SeCl
SeCl, AsCl
GeCl
GeCl, AsCl
SeCl, AsCl
GeCl
NCI. OC1
MgCl
SiCl. MgCl
SiCl
ZrS
CaS
MoS
MoS
SeS
SeS
SeS
GeS
SeS,
SO
A1S
PS
SS, :
AgC
CdC
CuC
SnC
SnC
SnC
SnC
MoC
MoC
MoC. ZrC
GeS MoC. ZrC
ArC
KC
ArC
CaC
TiC
VC
S02H CrC
206Fb
2°7pK
»4»
SS
SS
%?
60.
62
'Ni
Ni
MO
ArNa
KO
WO
WO
WO
WO
CaO
CaO
TiO
ArOH
WOH
WOH
WOH
TaOH
KOH
CaOH
ScOH
KN
WN
WN
UN
CaN
TiN
TiN
NaS
NaCl
MgS
MgCl. NaCl SiS
AlCl. MgCl SiS
CaC
WC
WC
TiC
TiC
TiC. CrC
Sn"
C-14
10/91
-------
Analvte
61»«
78
82
76
77
74
Se
Se
Se
Se
Se
lol
109
205
'Tl
68
70
Zn
Oxygen
Inter.
ScO
TiO
ZnO
NiO
ZnO
NiO
NiO
NiO
ZrO
CIO
SO
TiO
TiO
CrO
VO
FeO
Hydroxyl
Inter.
CaOH
TiOH
CuOH
NiOH
CuOH
CoOH
NiOH
FeOH
ZrOH
MoOH
WOH
SOH
TiOH
TiOH
VOH
TiOH, Cr
CrOH
TABLE XIII (conc'd)
Nitrogen Chlorine Sulfur Carbon
Inter. Inter. Inter. Inter. Other,
TIN
TIN, CrN
ZnN
ZnN
ZnN
NiN
CuN
NiN
MoN
C1N
ArN
TiN, CrN
CrN
FeN
CrN
GeN
MgCl
SiCl, A1C1
ScCl, CaCl
CaCl. KC1
TiCl, ScCl
KC1
CaCl, ArCl
C1C1, KC1
GeCl
GeCl
SiS
SS
TiS
TiS
TiC
CrC
ZnC
ZnC
Sn-
TiS, CrS
CaS ZnC
ScS CuC
CaS NiC
AsS MoC
SeS MoC
CIO, C1N FS
SiCl, A1C1 SS
PCI, SiCl SS
PCI ArS
SCI CIS
C1C1 ArS
KC
ArC
CrC
FeC
FeC
MnC
NiC
Mo-
Ba-
Ba"
Note: The information provided in this table does not indicate that all of
the described interferences need to be tested. However, the table can be
consulted for informational purposes if unusual samples are encountered.
C-15
10/91
-------
TABLE XIV
MASS CHOICES FOR ELEMENTS THAT MUST BE MONITORED
EITHER DURING THE ANALYTICAL RUN OR IN A SEPARATE SCAN FOR ICP/MS
Boldface and underlined masses indicate Che Basses that
should have the most impact on data quality and the elemental
equations used to collect the data. Underlined
masses nost be monitored.
Element of interest
22 • Aluminum
121. 123 Antimony
21 . Arsenic
138, 137, 136, 135. 134, 132. 130 Barium
£ Beryllium
114. 112, 111, 110. 113. 116. 106, 108 Cadmium
42, 43, 44, 46, 48 Calcium
52,52,10,54 Chromium
£i Cobalt
i2, $5_ Copper
Si. 1&. 12, 58 Iron
208. 207. 206. 204 Lead
24, 21, 2i Magnesium
H Manganese
202, 200. 199, 201 Mercury
58, 60, 62, 6JL, 64 Nickel
3j9 Potassium
80. 21, 82, 2i, 22. 74 Selenium
107. 109 Silver
22 Sodium
205. 203 Thallium
51, SS. Vanadium
64, ii. 4S, 12, 70 Zinc
42 Krypton
72 Germanium
139 Lanthanum
140 Cerium
129 Xenon
118 Tin
105 Palladium
47, 49 Titanium
125 Tellurium
69 Gallium
35, 37 Chlorine
98. 96, 92, 91, 94 Molybdenum
NOTE: Although the only masses that must be monitored are underlined, it is
strongly recommended that the other elements be monitored to indicate other
potential molecular interferences that could affect the data quality.
C-16 10/91
-------
ANALYTICAL METHODS
PAGE
SECTION I - INTRODUCTION °-2
SECTION II - SAMPLE PRESERVATION AND HOLDING TIMES 0-3
PART A - PRESERVATION OF WATER SAMPLES D-3
PART B - HOLDING TIMES FOR WATER SAMPLES D-3
SECTIOH III - SAMPLE PREPARATION D-4
SECTION IV - SAMPLE ANALYSIS D-12
PART A - REAGENTS AND STANDARDS FOR METAL ANALYSIS
AND SAMPLE PREPARATION D-12
PART B - INDUCTIVELY COUPLED PLASMA-ATOMIC
EMISSION SPECTROMETRIC METHOD D-16
PART C - HYDRIDE GENERATION- ICP-ATOMIC EMISSION
SPECTROMETRIC METHOD D-23
PART D - GRAPHITE FURNACE AND FLAME ATOMIC ABSORPSION METHODS .. D-29
PART E - INDUCTIVELY COUPLED PLASMA-MASS SPECTROMETRY D-36
PART F - METHOD FOR MERCURY ANALYSIS IN WATER D-46
PART G - METHOD FOR TOTAL CYANIDE ANALYSIS IN WATER D-53
PART H - ION CHROMATOGRAPHY METHODS FOR N02/N03-N D-60
PART I - AUTOMATED COLORIMETRIC METHODS FOR
THE DETERMINATION OF NO2/N03-N D-64
PART J - ION SELECTIVE ELECTRODE METHOD FOR
THE DETERMINATION OF FLUORIDE D-68
D-l 10/91
-------
SECTION I
INTRODUCTION
The analytical method specified in Exhibit 0 nay be utilized as long as Che
documented instrument or method detection limits meet the Contract Required
Detection Limits (Exhibit C, Tables I and II). Analytical methods with
higher detection limits may be used only if the sample concentration exceeds
five times the documented detection limit of the instrument or method.
The sample for dissolved metal analysis will be filtered through a 0.450
membrane filter and preserved in the field before the samples are shipped to
the laboratory. All instrument calibration standards must be matrix matched
to the samples for dissolved metals. Matrix MtthlM BUS^ be applied without
affeecing che original sample '"?lVBf by more than ten percent.
All samples must initially be run undiluted (i.e., original sample or final
product of sample preparation procedure). When an analyte concentration
exceeds the calibrated or linear range, re-analysis for that analyte(s) is
required after appropriate dilution. The Contractor must use the lowest
dilution factor necessary to bring each analyte within the valid analytical
range (but not below the CRDL) and report the highest valid value for each
analyte. Unless the Contractor can submit proof that dilution was required
to attain valid results, both diluted and undiluted sample measurements must
be contained in the raw data.
Labware must be acid cleaned according to EPA's manual "Methods for Chemical
Analysis of Water and Wastes" or an equivalent procedure. Samples must be
opened and digested in a hood. Stock solutions for standards may be
purchased or made up as specified in Part A of Exhibit D. All sample
dilutions shall be made with deionized water acidified to maintain constant
acid strength.
Before water sample preparation is initiated, the Contractor must check the
pH of all water samples, and note the pH in the sample preparation log.
Unless otherwise instructed by SHO, all samples must be mixed thoroughly
prior to aliquoting for analysis or digestion.
Background corrections are required for all furnace AA measurements. Each
furnace analysis requires at least two burns, except for full Method of
Standard Additions (MSA) .
All ICP, ICP-Hydride, and ICP/MS measurements shall require a minimum of two
complete replicate exposures. Exposures for all samples and quality
assurance measurements must be reported in the raw data in concentration
units; intensities are not acceptable. The average of the exposures must be
used for standardization, sample analysis, and in the reporting as specified
in Exhibit B.
D-2 10/91
-------
SECTION II
SAMPLE PRESERVATION AND HOLDING TIMES
A. PRESERVATION OP WATER SAMPLES
Measurement
Parameter Container(l> Preservative(2)
Metals(3) P,G HNO3 to pH <2
Cyanide, total P,G 0.6g ascorbic acid(4)
and amenable NaOH to pH >12
to chlorination Cool, maintain at
4*C(±2'C)
until analysis
N02/N03-N P.G H2S04 to pH <2
Fluoride P,G Cool, maintain at 4*C(± 2'C)
FOOTNOTES:
(1) Polyethylene (P) or glass (G).
(2) Sample preservation is performed by the sampler immediately upon
sample collection.
(3) Samples are filtered immediately on-site by the sampler before
adding preservative for dissolved metals.
(4) Only used in the presence of residual chlorine.
B. HOLDING TIMES FOR WATER SAMPLES
Following are the maximum sample holding times allowable under this
contract. To be compliant with this contract, the Contractor must
analyze samples within these times even if these times are less than the
maximum data submission times allowed in this contract.
No. of Days Following
Sample Receipt
Analvte bv Contractor
Mercury 26 days
Metals (other than mercury) 180 days
Cyanide 12 days
N02/N03-N 12 days
Fluoride 26 days
The Contractor must verify that the samples have been preserved properly
using wide range pH paper. If the results of such verification do not
conform to the requirements stated in A for preservation or in B for
holding time, the Contractor must contact SMO for instructions before
proceeding any further.
D-3 10/91
-------
SECTION III
SAMPLE PREPARATION
Before collecting samples, a decision must be made by the data user as to the
type of data desired, i.e., dissolved or total constituent analysis. This
information will be included on the traffic report and the following
preparation techniques shall be used for analysis under this contract.
All samples and standards (including QA/QC standards) must be matrix matched
before analysis. Matrix matching must be applied without affecting the
original sample vrtl|iiffc bv more than ten percent.
1. DISSOLVED METAT.S PATER SAMPLE PREPARATION
For the determination of dissolved constituents the sample must be
filtered through a 0.45 u membrane filter and preserved in the field.
This will be performed by the sampling team and recorded on the traffic
report form. Analysis performed on a sample so treated shall be
reported as "dissolved* concentrations.
2. TOTAT, *ET*T-«t WATER SAHPLJ PREPARATION USING HOT PLATE DIGESTION
2.1 ACID DIGESTION PROCEDURE FOR FURNACE ATOMIC ABSORPTION ANALYSIS
Shake sample and transfer 100 mL of well-mixed sample to a 250-mL
beaker, add 1 mL of (1+1) HNO3 and 2 mL 30% ^2 Co the sample. Cover
with watch glass or similar cover and heat on a steam bath or hoc plate
for 2 hours at 95*C or until sample volume is reduced to between 25 and
50 mL, making certain sample does not boil. Cool sample and filter Co
remove insoluble material. (NOTE: In place of filtering, the sample,
after dilution and mixing, may be centrifuged or allowed to setcle by
gravity overnight to remove insoluble material.) Adjust sample volume
to 100 mL with deionized distilled water. The sample is now ready for
analysis.
Concentrations so determined shall be reported as "total".
If Sb is to be determined by furnace AA, use the digestate prepared for
ICP/flame AA analysis.
2.2 ACID DIGESTION PROCEDURE FOR ICP, HYICF AND FLAME AA ANALYSES
Shake sample and transfer 100 mL of veil-mixed sample to a 250-mL
beaker, add 2 mL of (1+1) HN03 and 10 mL of (1+1) HC1 Co the sample.
Cover with watch glass or similar cover and heat on a steam bath or hot
place for 2 hours at 95*C or until sample volume is reduced to between
25 and 50 mL, making certain sample does not boil. Cool sample and
filter to remove insoluble material. (NOTE: In place of filCering,
the sample, after dilution and mixing, may be centrifuged or allowed to
settle by gravity overnight to remove insoluble material.) Adjust
sample volume to 100 mL with deionized distilled water. The sample is
now ready for analysis.
D-4 10/91
-------
Concentrations so determined shall be reported as "total*.
2.3. ACID DIGESTION PROCEDURE FOR ICP/MS ANALYSIS
Shake the sample and transfer 100 mL of well-mixed sample to a 250 mL
beaker, add 1.0 mL of (1+1) HN03 and 2 mL of 30% H202 to the saaple.
Cover with a watch glass or similar cover and heat on a steam bath or
hot plate for 2 hours at 95*C (temperature should be monitored with a
thernameter) or until sample volume is reduced to between 25 and 50 mL,
making certain that the sample does not boil. Cool the sample and
filter » I., ernove insoluble material. Adjust the sample volume to 100
mL with «aJV. Typ . I water. The sample is now ready for analysis.
The sample preparation procedure for ICP-AES must be used for
quantitation if this digestate contains more than 30 ug/L of silver, or
more.than 100 ug/L of antimony.
Concentrations so determined shall be reported as "total".
3. TOTAL METAT-g WATER SAMP*-* PREPARATION PS IRC MICROWAVE DIGESTION
3.1 SCOPE AND APPLICATION
This method is an acid digestion procedure using microwave energy to
prepare water samples for analysis by GFAA, ICP, and/or ICP/MS for the
following metals:
Aluminum Chromium Potassium*
Antimony Cobalt Selenium
Arsenic Copper Silver
Barium Iron Sodium*
Beryllium Lead Thallium
Cadmium Magnesium* Vanadium
Calcium* Manganese Zinc
Nickel
*NOTE:All elements except for calcium, magnesium, potassium, and
sodium may be analyzed by ICP/MS.
3.2 SUMMARY OF METHOD
3.2.1 A representative 45 mL water sample is digested in nitric acid.
The digestate is then filtered to remove insoluble material.
(NOTE: In place of filtering, the sample may be centrifuged or
allowed to settle by gravity overnight to remove insoluble
material). If filtering is required, the sample is processed
without volume correction since the final volume is identical
to the initial volume in closed vessel digestions.
D-5 10/91
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3.3 APPARATUS AND MATERIALS (MICROWAVE)
3.3.1 Cornercial kitchen or home-use microwave ovens shall not be
used for the digestion of samples under this contract. The
oven cavity must be corrosion resistant and well ventilated.
All electronics must be protected against corrosion for safe
operation.
3.3.2 Microwave oven with programmable power settings up to at least
600 watts.
3.3.3 The system must use PFA TeflonR digestion vessels (60 to 120 mL
capacity) capable of withstanding pressures of up to 100 psi.
Pressure venting vessels capable of controlled pressure relief
at pressures exceeding 100 psi.
3.3.A A double ported TeflonR PFA overflow vessel (60 or 120 mL
capacity).
3.3.5 A rotating table must be used to ensure homogeneous
distribution of microwave radiation within the oven.
3.4 MICROWAVE CALIBRATION PROCEDURE
3.4.1 The calibration procedure is a critical step prior to the use
of any microwave unit. In order that absolute power settings
may be interchanged from one microwave unit to another, the
actual delivered power must be determined.
Calibration of a laboratory microwave unit depends on the type
of electronic system used by the manufacturer. If the unit has
a precise and accurate linear relationship between the output
power and the scale used in controlling the microwave unit,
then the calibration can be a single-point calibration at
maximum power. If the unit is not accurate or precise for some
portion of the controlling scale, then a multiple point
calibration is necessary. If the unit power calibration needs
multiple point calibration, then the point where linearity
begins must be identified. For example: a calibracion at 100,
99, 98, 97, 95, 90, 80, 70, 60, and 50% power settings can be
applied and the data plotted. The nonlinear portion of the
calibration curve can be excluded or restricted in use. Each
percent is equivalent to approximately 5.5 - 6.5 W and becomes
che smallest unit of power that can be controlled. If 20 - 40
U are contained from 99-100%, that portion of che microwave
calibration is not controllable by 3-7 times that of che linear
portion of the control scale and will prevent duplication of
precise power conditions specified in that portion of Che power
scale.
The following equation evaluates che power available for
heating in a microwave cavity. This is accomplished by
measuring the temperature rise in 1 Kg of water exposed co
electromagnetic radiation for a fixed period amount of time.
D-6 10/91
-------
Measurements are made on weighed replicates (5 replicates) of
one kilogram samples of room temperature distilled water in
thick-walled microwave transparent (Teflon*) vessels. The
containers must be circulated continuously through the field
for at least two (2) minutes at full power. Th
-------
Cp - The heat capacity, thenul capacity or specific
heat, (cal-g^-'C*1 - 1.0 for water).
M - The mass of the saaple in grams (g).
T - Tf-Ti in -C.
t - Tine in seconds (s).
Derive an equation for the linear portion of the
calibration range and determine the equivalent value
in watts of the arbitrary setting scale. Use the
actual power in watts to determine the appropriate
setting of the particular microwave unit being used.
Each microwave unit will have its own setting that
corresponds to the actual power delivered to the
samples.
3.4.3 Cleaning Procedure
3.4.3.1 The initial cleaning of the FFA vessels*:
3.4.3.1.1 Prior to first use - New vessels must
be annealed before they are used. A
pretreatment/cleaning procedure must be
followed. This procedure calls for
heating the vessels for 96 hours at
200*C. The vessels must be
disassembled during annealing and the
sealing surfaces (the top of the vessel
or its rim) must not be used to support
the vessel during annealing.
3.4.3.1.2 Rinse in ASTH Type I water.
3.4.3.1.3 Immerse in 1:1 HC1 for a minimum of 3
hours after the cleaning bath has
reached a temperature just below
boiling.
3.4.3.1.4 Rinse in ASTH Type I water.
3.4.3.1.5 Immerse in 1:1 HNC>3 for a minimum of 3
hours after the cleaning bath has
reached a temperature just below
boiling.
3.4.3.1.6 The vessels are then rinsed with
copious amounts of ASTM Type I water
prior to use for any analyses under
this contract.
Note: All precautions must be taken to avoid preparation
blank contamination.
D-8 10/91
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3.5 CLEANING PROCEDURE BETWEEN SAMPLE DIGESTIONS
3.5.1 Wash entire vessel in hot water using laboratory-grade
nonphosphcte detergent.
3.5.2 Rinse wich 1:1 nitric acid.
3.5.3 Rinse three times with ASTM Type I water. If contaminants are
found in the preparation blank, it is manadatory that steps
3.4.3.1.2 through 3.4.3.1.6 be strictly adhered to.
3.6 DIGESTION PROCEDURE FOR MICROWAVE
3.6.1 45 mL of the sample are measured into TeflonR digestion vessels
using volumetric glassware. 5 mL of high purity HNO3 are added
to the digestion vessels and the weight recorded to 0.02 g.
3.6.2 The caps with the pressure release valves are placed on the
vessels hand tight and then tightened, using constant torque,
to 12 ft.-Ibs. Place 5 sample vessels in the carousel, evenly
spaced around its periphery in the microwave unit. Venting
tubes connect each sample vessel with a collection vessel.
Each sample vessel is attached to a clean, double-ported vessel
to collect any sample expelled from the sample vessel in the
event of over pressurization. Assembly of the vessels into the
coracle may be done inside or outside the microwave. This
procedure is energy balanced for five 45 mL water samples (each
with 5 mL of acid) to produce consistent conditions and prevent
alteration of the conditions. The initial temperature of the
samples should be 24 + 1*C. Blanks must have 45 mL of
deionized water and the same amount of acid to be added to the
microwave as a reagent blank.
3.6.3 Power Programming of Nitric Acid:
The 5 samples of 45 mL water and 5 mL nitric acid are
irradiated for 10 minutes at 545 V and immediately cycled to
the second program for 10 minutes at 344 W (BASED ON THE
CALIBRATION OF THE MICROWAVE UNIT AS PREVIOUSLY DESCRIBED).
This program brings the samples to 160 + 4*C in 10 minutes and
then causes a .slow rise in temperature between 165-170'C during
the second 10 minutes.
3.6.4 Following the 20 minute program, the samples are left to cool
in the microwave unit for 5 minutes, with the exhaust fan ON.
The samples and/or carousel may then be removed from the
microwave unit. Before opening the vessels, let cool until
they are no longer hot to the touch.
3.6.5 After the sample vessel has cooled, weigh the sample vessel and
compare to the initial weight as reported in the preparation
log. Any sample vessel exhibiting a < 0.5 g loss must have any
excess sample from the associated collection vessel added to
D-9 10/91
-------
the original sample vessel before proceeding with the sanple
preparation. Any sample vessel exhibiting a > 0.5 g loss must
be identified in the preparation log and the sample redigested.
3.6.6 Sample Filtration:
The digested samples are shaken well to mix in any condensate
within the digestion vessel before being opened. The digestate
are then filtered into 50 mL glass volumetric flasks through
ultra-clean filter paper and diluted to 50 mL (if necessary) .
The samples are now ready for analysis. The sample results
must be corrected by a factor of 1.11 in order to report final
concentration valves based on an initial volume of 45 mL.
Concentrations so determined shall be reported as "total".
4. PICgSTIOH PROCEDURE Pffl HKR?PRY ANALYSIS
Because the digestion procedure for mercury is an integral part of the
analysis system, it is discussed in Part F of the Sample Analysis
Section (Section IV).
5.
5.1 Place 500 mL of sample, or an aliquot diluted to 500 mL, in the 1 liter
boiling flask. Add 50 mL of sodium hydroxide to the absorbing tube and
dilute if necessary with ASTM Type I water to obtain an adequate depth
of liquid in the absorber. Connect the boiling flask, condenser,
absorber and tap in the train.
5.2 Start a slow stream of air entering the boiling flask by adjusting the
vacuum source. Adjust the vacuum so that approximately one bubble of
air per second enters the boiling flask through the air inlet tube.
NOTE: The bubble rate will not remain constant after the reagents have
been added and while heat is being applied to the flask. It will be
necessary to readjust the air rate occasionally to prevent the solution
in the boiling flask from backing up into the air inlet tube.
5.3 Slowly add 25 mL concentrated sulfuric acid through the air inlet tube.
Rinse the tube with ASTM Type I water ana allow the airflow to mix the
flask contents for 3 minutes. Pour 20 mL of magnesium chloride
solution into the air inlet and wash down with a stream of water.
5.4 Heat the solution to boiling, taking care to prevent the solution from
backing up into and overflowing from the air inlet tube. Reflux for
one hour. Turn off heat and continue the airflow for at least 15
minutes. After cooling the boiling flask, disconnect the absorber and
close off the vacuum source.
5.5 Drain the solution from the absorber into a 250 mL volumetric flask and
bring up to volume with ASTM Type I water washings from the absorber
tube.
D-10 10/91
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5.6 The samples are now ready for analysis. The sample results mist be
corrected for by a factor of 2 in order to report final concentration
based on an initial volume of 500 ml. If the initial volume is less
than 500 mL, the sample must be diluted to 500 mL and an appropriate
dilution factor must be indicated.
6. PREPARATION PROCEDURE FOR ION CHROMATOGRAPHT METHOD
Filtration of the sample and reagents is required. The saaple matrix
should be matched with all blanks, standards, and quality control
samples to avoid inaccuracies resulting from possible standard curve
deviation. The preparation procedure for the Ion Chromatography method
is an integral part of the analysis system and is discussed in full in
Part H of the Sample Analysis Section (Section IV) .
7. P»*PABATIOH PROCEDURE FOR AUTOMATED COLORPffiTRI? METHODS
Filtration of the sample and reagents is required. The sample matrix
should be matched with all blanks, standards, and quality control
samples to avoid inaccuracies resulting from possible standard curve
deviation. The preparation procedure for using Automated Colorimetric
Methods is an integral part of the analysis system and is discussed in
full in Part I of the Sample Analysis Section (Section IV).
8. PREPARATION PROCEDURE FOR TOM fiETrgCTTint gT^CTRODE METHOD
A pH 5 buffer containing a strong chelating agent must be added to all
samples to eliminate interferences caused by pH and complexes forming.
The preparation procedure for using the Ion Selective Electrode method
is an integral part of the analysis system and is discussed in full in
Part J of the Sample Analysis Section (Section IV) .
D-ll 10/91
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Exhibit D Section IV
SECTION IV
SAMPLE ANALYSIS
PART A - REAGENTS AND STANDARDS FOR METALS ANALYSIS AND SAMPLE PREPARATION
1. REAGENTS AND STANDARDS
1.1 Acids used in the preparation of standards ancti
-------
Exhibit D Section IV
Metal
weight (mg)
Concentration (rag/L) - —- —-—
volume (L)
Metal salts
weight (mg) x mole fraction
Concentration (mg/L) -
volume (L)
NOTE: The recommended amounts of the starting materials specified for
the following stock solutions are dependent upon the stoichionetry of
the materials used as starting materials. Actual assay values of the
starting materials should be used and the actual amounts corrected
accordingly.
1.3.1 Aluminum solution, stock, 1 aL - 100 ug Al: Dissolve 1.3903 g
A1(NO3)3-9H20 in 10 mL ASTM Type I water with 10 mL. HN03.
Dilute to 1,000 mL with ASTM Type I water.
1.3.2 Antimony solution, stock, 1 mL - 100 ug Sb: Dissolve 0.1197 g
Sb2C>3 in 5 mL ASTM Type I water containing 0.1233 g C^OgHg
(tartaric acid), add SOO mL ASTM Type I water, add 1 aL cone.
HN<>3 and dilute to 1,000 mL with ASTM Type I water.
1.3.3 Arsenic solution, stock, 1 mL - 100 ug As: Dissolve 0.1320 g
of AS203 in 100 mL of ASTM Type I water containing 0.45 g
HH^OH. Acidify the solution with 12 mL cone. HN03 and dilute
to 1,000 mL with ASTM Type I water.
1.3.4 Barium solution, stock, 1 mL - 100 ug Ba: Dissolve 0.1437 g
BaCO3 in 10 mL ASTM Type I water with 10 mL cone. HNC>3. After
dissolution is complete, warm the solution to degas. Dilute to
1,000 mL with ASTM Type I water.
1.3.5 Beryllium solution, stock, 1 mL - 100 ug Be: Do not dry.
Dissolve 4.5086 g BeO(C2H302)g in ASTM Type I water, add 10.0
mL cone. HNO} and dilute to 1,000 mL with ASTM Type I water.
1.3.6 Cadmium solution, stock, 1 mL - 100 ug Cd: Dissolve 0.1142 g
CdO in a minimum amount of (1+1) HN03. Heat to increase rate
of dissolution. Add 10.0 mL cone. HNO3 and dilute to 1,000 mL
with ASTM Type I water.
1.3.7 Calcium solution, stock, 1 mL - 100 ug Ca: Suspend 0.2498 g
CaCC>3 dried at 180 *C for 1 h before weighing in ASTM Type I
water and dissolve cautiously with a minimum amount of (1+1)
HN03- After dissolution is complete, warm the solution to
degas. Add 10.0 mL cone. HNO3 and dilute to 1,000 mL with ASTM
Type I water.
D-13 10/91
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Exhibit 0 Section IV
«
1.3.8 Chromium solution, stock, 1 mL - 100 ug Cr: Dissolve 0.2424 g
of (NH4>2Cr207 in ASTM Type I water. Reduce the chromium with
a few drops of hydrazine (NH^W^), exhibited by the color
change of the solution from orange to green. When solution is
complete, acidify with 10 mL cone. HNO3 and dilute to 1,000 mL
with ASTM Type I water.
1.3.9 Cobalt solution, stock, 1 mL - 100 ug Co: Dissolve 0.1000 g of
cobalt metal in a minimum amount of (1+1) HN03. Add 10.0 mL
cone. HN03 and dilute to 1,00 mL with ASTM Type I water.
1.3.10 Copper solution, stock, 1 mL - 100 ug Cu: Dissolve 0.1000 g Cu
in a minimum amount of (1+1) HN03. Add 10.0 mL cone. HN03 and
dilute to 1,000 mL with ASTM Type I water.
1.3.11 Iron solution, stock, 1 mL - 100 ug Fe: Dissolve 0.1000 g Fe
in a minimum amount of (1+1) HN03. Add 10.0 mL cone. HH03 and
dilute to 1,000 mL with ASTM Type I wacer.
1.3.12 Lead solution, stock, 1 mL - 100 ug Pb: Dissolve 0.1599 g
Pb(N03)2 in a minimum amount of (1+1) HN03. Add 10.0 mL of
cone. HN03 and dilute to 1,000 mL with ASTM Type I wacer.
1.3.13 Magnesium solution, stock, 1 aL - 100 ug Mg: Dissolve 0.1658 g
MgO in a minimum amount of (1+1) HN03. Add 10.0 mL cone. HN03
and dilute to 1,000 mL with ASTM Type I water.
1.3.14 Manganese solution, stock. 1 mL - 100 ug Mn: Dissolve 0.3149 g
of manganese acetate Mn (€2^2)2 in ASTM Type 1 water. Add
10.0 mL of cone. HN03 and dilute to 1.000 mL with ASTM Type I
water.
1.3.15 Mercury solution, stock, 1 mL - 100 ug Hg: Dissolve 0.1708 g
mercury (II) nitrate Hg(N03)2"(H20) in 75 oL of ASTM Type I
water. Add 10 mL of cone. HN03 and dilute to 1,000 mL with
ASTM Type I water.
1.3.16 Nickel solution, stock, 1 mL - 100 ug Ni: Dissolve 0.1000 g of
nickel metal in 10 mL hoc cone.' HN03> cool and dilute to 1,000
mL with ASTM Type I water.
1.3.17 Silver solution, stock, 1 mL - 100 ug Ag: Dissolve 0.1575 g
AgN03 in 100 mL of ASTM Type 1 water and 10 mL cone. HN03.
Dilute to 1000 mL with ASTM Type 1 water.
1.3.18 Thallium solution, stock, 1 mL - 100 ug Tl: Dissolve 0.1303 g
T1N03 in ASTM Type I water. Add 10.0 mL cone. HN03 and dilute
to 1,000 mL with ASTM Type I water.
1.3.19 Vanadium solution, stock, 1 mL - 100 ug V: Dissolve 0.2296 g
NH^V03 in a minimum amount of cone. HNO3. Heat to increase
rate of dissolution. Add 10.0 mL cone. HN03 and dilute to
1,000 mL with ASTM Type I water.
D-14 10/91
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Exhibit D Section IV
V "*
1.3.20 Zinc solution, stock, 1 mL - 100 ug Zn: Dissolve 0.1245 g ZnO
in a minimum amount of dilute HNO3- Add 10.0 mL cone. HN(>3 and
dilute to 1,000 mL with ASTM Type I water.
1.4 In the determination of trace elements, containers can introduce either
positive or negative errors in the measurement of trace elements by (a)
contributing contaminants through leaching or surface desorption and
(b) depleting concentrations through adsorption. Thus the collection
and treatment of the samples prior to analysis require particular
attention. The following cleaning treatment sequence has been
determined to be adequate to minimize contamination in the sample
bottles, whether borosilicate glass, linear polyethylene, or Teflon:
detergent, Type II water, 1+1 hydrochloric acid, ASTM Type I water, 1+1
nitric acid, and Type I water.
Note: Chromic acid mist not be used because chromium is one of the contract
required analytes, and its use may lead to cross-contamination.
1.5 Three types of blanks are required for the analysis. The calibration
blank is used in establishing the calibration curve, the preparation
blank is used to monitor for possible contamination resulting from the
sample preparation procedure, and the rinse blank is used to flush the
system between-all samples and standards.
1.5.1 The calibration blank must be matrix matched to the standards.
1.5.2 The preparation blank must contain all the reagents in the same
volumes as used in processing the samples. The reagent blank
must be carried through the complete procedure and contain the
same acid concentration in the final solution as the sample
solutions used for analysis.
1.5.3 The rinse blank consists of the appropriate acid in ASTM Type I
water. Prepare a sufficient quantity to flush the system
between standards and samples.
1.6 The instrument check standard is the Initial and Continuing Calibration
Verification solution (ICV and CCV) which is prepared by the analyst by
combining compatible elements at concentrations equivalent to the
midpoint of their respective calibration ranges. This solution must be
prepared in the same acid matrix as the calibration standards.
1.7 The Interference Check Solution(s) (ICS) is prepared to contain known
concentrations of interfering elements that will demonstrate the
magnitude of interferences and provide an adequate test of any
corrections. The ICS is used to verify that the interference levels
are corrected by the data system within quality control limits.
1.7.1 Stock solutions for preparing ICS A and AB may be provided if
available. Otherwise, refer to Exhibit C, Table V. They must
be diluted tenfold (1+9) before use according to the
instructions provided. The final ICS A and AB must be prepared
weekly.
D-15 10/91
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Exhibit D ICF-AES
PART B
IHDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROMETRIC METHOD
1. SCOPE AND APPLICATION
1.1 Table I, in Exhibit C, lists elements along with the Contract Required
Detection Liait for the analysis of metals in low concentration waters.
Actual working detected limits are saaple dependent and as the sample
matrix varies, these concentrations may also vary. Appropriate steps
must be taken in all analyses to ensure that potential interferences
are taken into account.
2. SUMMARY OF METHOD
2.1 The method describes a technique for the simultaneous or sequential
multielement determination of trace elements in solution. The basis of
the method is the measurement of atomic emission by an optical
spectroscopic technique. Samples are nebulized and the aerosol that is
produced is transported to the plasma torch where excitation occurs.
Characteristic atomic-line emission spectra are produced by a radio-
frequency inductively coupled plasma (ICP). The spectra are dispersed
by a grating spectrometer and the intensities of the line are monitored
by photomultiplier tubes. The photocurrents from the photomultiplier
tubes are processed and controlled by a computer system. A background
correction technique is required to compensate for variable background
contribution to the determination of trace elements. Background must
be measured adjacent to analyte lines on samples during analysis. The
position selected for the background intensity measurement, on either
or both sides of the analytical line, will be determined by the
complexity of the spectrum adjacent to the analyte line. The position
used must be free of spectral interference and reflect the same change
in background intensity as occurs at the analyte wavelength measured.
Background correction is not required in cases of line broadening where
a background correction measurement would actually degrade the
analytical result. The possibility of additional interferences named
in 3 should also be recognized and appropriate corrections made.
3.
3.1 Several types of interference effects may contribute to inaccuracies in
the determination of trace elements. They can be summarized as
follows:
3.1.1 Spectral interferences can be categorized as
3.1.1.1 Overlap of a spectral line from another element;
3.1.1.2 Unresolved overlap of molecular band spectra;
3.1.1.3 Background contribution from continuous or
recombination phenomena; and
D-16 10/91
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Exhibit D ICP-AES
3.1.1.4 Background contribution from stray light from the
line emission of high concentration elements.
The first of these effects can be compensated by
utilizing a computer correction of the raw data,
requiring the monitoring and measurement of the
interfering element. The second effect may require
selection of an alternate wavelength. The third and
fourth effects can usually be compensated by a
''-• kground correction adjacent to the analyte line.
lit -Wit-inn, users of simultaneous multi-element
iiistrunpfxiration oust assume the responsibility of
verifying the absence of spectral interference from
an element that could occur in a sample but for
which there is no channel in the instrument array.
Listed in Table VI, Exhibit C, are some interference
effects for recommended wavelengths. The data in
Table VI, Exhibit C, are intended for use only as a
rudimentary guide for the indication of potential
spectral interferences. For this purpose, linear
relations between concentration and intensity for
the analytes and the interferents can be assumed.
The interference information, which was collected at
the Ames Laboratory, is expressed as analyte
concentration equivalents (i.e., false analyte
concentrations) arising from 100 mg/L of the
interferent element.
The suggested use of this information is as follows:
Assume that arsenic (at 193.696 nm) is to be
determined in a. sample containing approximately 10
mg/L of aluminum. According to Table VI, Exhibit C,
100 mg/L of aluminum would yield a false signal for
arsenic equivalent to approximately 1.3 mg/L.
Therefore, 10 mg/L of aluminum would result in a
false signal for arsenic equivalent to approximately
0.13 mg/L. The reader is cautioned that other
analytical systems may exhibit somewhat different
levels of interference than those shown in Table VI,
Exhibit C, and that the interference effects must be
evaluated for each individual system. Only those
interferents listed were investigated and the blank
spaces in Table VI, Exhibit C, indicate that
measurable interferences were not observed from the
interferenc concentrations listed in Table V,
Exhibit C. Generally, interferences were
discernible if they produced peaks or background
shifts corresponding to 2-5% of the peaks generated
by the analyte concentrations also listed in Table
V, Exhibit C. At present, information on the listed
D-17 io/91
-------
Exhibit D ICP-AES
silver and potassium wavelengths are not available
but it has been reported that second order energy
from Che magnesium 383.231 nm wavelength interferes
wich the listed potassium line at 766.491 nm.
3.1.2 Physical interferences are generally considered to be effects
associated with the sample nebulization and transport
processes. Such properties as change in viscosity and surface
tension can cause significant inaccuracies especially in
samples which may contain high dissolved solids and/or acid
concentrations. The use of a peristaltic pump may lessen these
interferences. If these types of interferences are operative,
they must be reduced by dilution of the sample and/or
utilization of standard addition techniques. Another problem
which can occur from high dissolved solids is salt buildup at
the tip of the nebulizer. This affects aerosol flow rate
causing instrumental drift.
Vetting the argon prior to nebulization, the use of a tip
washer, or sample dilution have been used to control this
problem. Also, it has been reported that better control of the
argon flow rate improves instrument performance. This is
accomplished with the use of mass flow controllers.
3.1.3 Chemical interferences are characterized by molecular compound
formation, ionization effects and solute vaporization effects.
Normally these effects are not pronounced with the ICP
technique, however, if observed they can be minimized by
careful selection of operating conditions (that is, incident
power, observation position, and so forth), by buffering of the
sample, by matrix matching, and by standard addition
procedures. These types of interferences can be highly
dependent on matrix type and the specific analyte element.
4.
4.1 Inductively Coupled Plasma-Atomic Emission Spectrometer.
4.1.1 Computer controlled atomic emission spectrometer with
background correction.
4.1.2 Radio frequency generator.
4.1.3 Argon gas supply, welding grade or better.
4 . 2 Operational Requirements
4.2.1 System configuration -- Because of the differences between
various makes and models of satisfactory instruments, no
detailed operating instructions can be provided. Instead, the
analyst should follow the instructions provided by the
manufacturer of the particular instrument. Sensitivity,
instrumental detection limit, precision, linear dynamic range,
and interference effects must be investigated and established
D-18 10/91
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Exhibit D ICP-£S
-
for each individual analyte line on that particular instrument.
All measurements must be within the instrument linear range
where correction factors are valid.
IT IS THE RESPONSIBILITY OF THE ANALYST TO VERIFY THAT THE
INSTRUMENT CONFIGURATION AND OPERATING CONDITIONS USED SATISFY
THE ANALYTICAL REQUIREMENTS SET FORTH IN THIS METHOD AND TO
MAINTAIN QUALITY CONTROL DATA CONFIRMING INSTRUMENT PERFORMANCE
AND ANALYTICAL RESULTS.
The data must include hardcopies or computer readable storage
•edia which can be readily examined by an audit teaa. The data
oust demonstrate the presence or absence of all spectral
interferences, including, but not limited to, the ones listed
in Table VI of Exhibit C. The data must demonstrate defendable
background correction points. This applies to simultaneous and
sequential ICP instruments. Sequential ICP data must
demonstrate the ability to select the correct peak from a
spectrum in which nearby peaks from interferents are present.
5. ^BACEJTS AND STANDARDS (SEE PART A)
5.1 Matrix matching, with the samples, is mandatory for all blanks,
standards and quality control samples, to avoid inaccurate
concentration values due to possible standard curve deviations.
S.2 Mixed calibration standard solutions for ICP -• Prepare nixed
calibration standard solutions by combining appropriate volumes of the
stock solutions, see PART A, in volumetric flasks. Add 2 mL of (1+1)
HN03 and 10 mL of (1+1) HC1 and dilute to 100 mL with ASTM Type I
water. Prior to preparing the mixed standards, each stock solution
should be analyzed separately to determine possible spectral
interference or the presence of impurities. Care should be taken when
preparing the mixed standards that the elements are compatible and
stable. Transfer the mixed standard solutions to a FEP fluorocarbon or
unused polyethylene bottle for storage. Fresh mixed standards should
be prepared as needed with the realization that concentration can
change on aging. Calibration standards must be initially verified
using a quality control sample and monitored weekly for stability.
Although not specifically required, some typical calibration standard
combinations follow when using those specific wavelengths listed in
Table 1.
5.2.1 Mixed standard solution I - - Manganese, beryllium, cadmium,
lead, and zinc.
5.2.2 Mixed standard solution II - - Barium, copper, iron, vanadium,
and cobalt.
5.2.3 Mixed standard solution III - - Molybdenum, silica, arsenic,
and selenium.
D-19 10/91
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. Exhibit 0 ICP-AES
5.2.4 Mixed standard solution IV • - Calcium, sodium, potassium,
aluminum, chromium, and nickel.
5.2.5 Mixed standard solution V - - Antimony, boron, magnesium,
silver, and thallium.
NOTE: If the addition of silver to the recommended acid
combination results in an initial precipitation, add 15 mL of
ASTM Type I water and warm the flask until the solution clears.
Cool and dilute to 100 mL with ASTM Type I water. For this
acid combination the silver concentration should be limited to
2 mg/L. Silver under these conditions is stable in a tap water
matrix for 30 days. Higher concentrations of silver require
additional HC1.
5.3 Two types of blanks are required for ICP analysis; the calibration
blank is used in establishing the analytical curve while the
preparation blank is used to correct for possible contamination
resulting from varying amounts of the acids used in the sample
processing.
5.3.1 The calibration blank is prepared by diluting 2 mL of (1+1)
HNO3 and 10 mL of (1+1) HC1 to 100 mL with ASTM Type I water.
Prepare sufficient quantity to be used to flush the system
between standards and samples.
5.3.2 The preparation blank must contain all the reagents and in the
same volume as used in the processing of the samples. The
reagent blank must be carried through the complete procedure
and contain the same acid concentration in the final solution
as the sample solution used for analysis (see Exhibit E).
5.4 The Interference Check Solution(s) (ICS) is prepared to contain known
concentrations of interfering elements that will demonstrate the
magnitude of interferences and provide an adequate test of any
corrections. The ICS is prepared by the analyst, if not previously
provided (Exhibit E). The ICS is used to verify that the interference
levels are corrected by adequate background correction and within
quality control limits.
6. PROCEDURE
6.1 Set up instrument with proper operating parameters established in
Section 4.2. The instrument must be allowed to become thermally stable
before beginning. This usually requires at least 30 min. of operation
prior to calibration.
6.2 Initiate appropriate operating configuration of computer.
6.3 Calibration and Sample Analysis
6.3.1 Profile and calibrate instrument according to instrument
manufacturer's recommended procedures, using matrix matched,
mixed calibration standard solutions such as those described in
D-20 10/91
-------
7.
Exhibit D ICP-AES
5.1. Calibrate the instrument for the analytes of interest
using the calibration blank and at least a single standard.
Flush the system with the calibration blank between each
standard. Use the average intensity of multiple exposures for
both standardization and sample analysis. A minimum of two
replicate exposures are required. The raw data must include the
concentrations of elements in each integration as well as the
average .
6.3.2 Begin the sample run flushing the system with the calibration
blank solution between each sample.
6.3.3 Dilute and reanalyze samples that are more concentrated than
the linear range for an analyte.
7.1 If dilutions were performed, the appropriate factor must be applied to
sample values.
7.2 Appropriate concentration units must be specified on the required
forms. The quantitative values shall be reported in units of
micrograms per liter (ug/L) for aqueous samples, NO other units are
acceptable.
8. Qfl^-'p'T COHTROL
8.1 Quality control must be performed as specified in Exhibit E.
8.2 All quality control (QC) data must be submitted with each data package
as specified in Exhibit B.
8,3. The interference check solution(s) (ICS) is prepared to contain known
concentrations of interfering elements that will demonstrate the
magnitude of interferences and provide an adequate test of any
corrections. The ICS is used to verify that the interference levels
are corrected by the data system within quality control limits.
9. REFERENCES
1. Annual Book of ASTM Standards, Part 31.
2. "Carcinogens - Working With Carcinogens," Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, Aug. 1977.
3. Garbarino, J.R. and Taylor, H.E., "An Inductively-Coupled Plasma Atomic
Emission Spectrometric Method for Routine Water Quality Testing,"
Applied Spectroscopy 33, No. 3(1979).
4. Handbook for Analytical Quality Control in Water and Uastewater
Laboratories, EPA-600/4-79-019 .
D-21 10/91
-------
Exhibit 0 ICP-AES
5. "Inductively Coupled Plasma-Atomic Emission Spectrometric Method of
Trace Elements Analysis of Water and Waste", Method 200.7 modified by
CLP Inorganic Data/Protocol Review Committee; original method by
Theodore D. Martin, EMSL/Cincinnati.
6. "Methods for Chemical Analysis of Water and Wastes." EPA- 600/4-79-020.
7. "OSHA Safety and Health Standards. General Industry," (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206, (Revised,
January 1976).
8 'Safe./ in Academic Chemistry Laboratories, American Chemical Society
?ubl..\!7rf-.ions, Committee on Chemical Safety, 3rd Edition, 1979.
9. Winefordner, J.D., "Trace Analysis: Spectroscopic Methods for
Elements," Chemical Analysis, Vol. 46, pp. 41-42.
10. Winge, R.K., V.J. Peterson, and V.A. Fassel, "Inductively Coupled
Plasma-Atomic Emission Spectroscopy Prominent Lines ,* EPA-600/4-79-017.
D-22 10/91
-------
Exhibit D Method 206.3
FART C
HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA-ATOMIC
EMISSION SPECTROMETRIC METHOD
1. SCOPE AND APPLICATION
1.1 This method covers the determination of antimony, arsenic and selenium
in low concentration waters.
1.2 The method is optimized for selenium, the least sensitive element,
which compromises the achievable sensitivities of antimony and arsenic.
1.3 The hydride generation system uses a high sodium borohydride to sample
ratio to minimize interferences. All sensitivities are somewhat
compromised by this approach.
1.4 Many spectral interferences common to the pneumatic nebulization ICF
analysis are eliminated.
1.5 Detection limits are lowered generally by a factor of ten over
pneumatic nebulization ICP analysis.
2. SUMMARY QP METHOD
2.1 The efficiency with which the volatile hydrides of antimony, arsenic
and selenium are generated is highly dependent on their oxidation
states. The volatile hydrides of arsenic and antimony are most
efficiently formed from +3 oxidation state while the volatile hydride
of selenium is most efficiently generated from the +4 oxidation step.
Aliquots of the sample are heated after the addition of an equal volume
of concentrated hydrochloric acid. The chloride-chlorine couple
developed reduces any selenium (VI) present to the selenium (IV)
oxidation state. Selenium must be present in the (IV) oxidation state
to form a hydride.
2.2 In a continuous flow system, the samples are reacted with sodium
borohydride, followed by potassium iodide, to produce the volatile
hydrides. The iodide-iodine couple reduces any arsenic (V) and
antimony (V) to their plus three oxidation states. This circumvents
the effect of the different hydride formation reaction rates of the
different oxidation states. The addition of the potassium iodide
after the addition of the sodium borohydride eliminates the formation
of elemental selenium by the iodide-iodine couple. It is the
laboratory's responsibility to verify that optimum conditions for
antimony, arsenic and selenium were obtained.
2.3 The hydrides are stripped from the sample by argon gas and swept into
the plasma of an Inductively Coupled Argon Plasma Optical Emission
Spectrometer. The resulting free atoms are excited into higher
electronic states. Atomic and ionic line emission spectra
characteristic of the particular elements are produced when the
electrons decay back to lower energy levels. The spectra are dispersed
by a spectrometer and the intensity of specific line radiation(s) are
D-23 10/91
-------
Exhibit D Method 206.3
monitored simultaneously or sequentially by photomultiplier tubes. The
photocurrents produced by the photomultiplier tubes will increase in
direct proportion to the concentration of the elements in the sample
within the linear range of a specific (emission line. The photocurrents
are processed and controlled by a computer systejs and related to
concentration through a calibration procedure.
3.
3.1 As discussed in Sections 2.1 and 2.2, proper adjustment of
oxidation states of the elements is important in obtaining accurate
results.
3.2 Some of the transition elements, especially copper, cause suppression
of the hydride formation by reacting to form insoluble salts. Selenium
is affected more than the other elements because transition metal
selenides are very insoluble. The high acid strength and high sodium
borohydride concentration help -to temper these effects. The use of the
method of standard additions compensates for these effects.
3.3 Spectral interferences common to the pneumatic nebulization analysis of
these three elements are eliminated because the interfering elements do
not form hydrides and thus are not introduced into, the plasma.
4. APPARATUS
4.1 Inductively Coupled Plasma-Atomic Emission Spectrometer
4.1.1 Computer-controlled inductively coupled argon plasma optical
emission spectrometer system. NOTE: A fast sequential scanning
instrument may be used if the Quality Control requirements set
forth in this method can be met, although a simultaneous
instrument is the instrument of choice.
4.1.2 Background correction capability.
4.1.3 Radiofrequency generator and coupling system.
4.1.4 Argon gas supply, welding grade or better.
4.1.5 Variable speed four channel peristaltic pump and pump tubing.
4.1.6 Hydride Manifold.
4.2 Operational Requirements
4.2.1 System Configuration -- Because of the differences between
various makes and models of satisfactory instruments, no
detailed operating instructions can be provided. Instead, the
analyst shall follow the instructions provided by the
manufacturer of the particular instrument. Sensitivity,
instrumental detection limit, precision, linear dynamic range,
and interference effects must be investigated and established
for each individual analyte line on that particular instrument.
D-24 10/91
-------
, Exhibit D Method 206.3
•
All measurements must be within the instrument linear range
where correction factors are valid.
IT IS THE RESPONSIBILITY OF THE ANALYST TO VERIFY THAT THE
INSTRUMENT CONFIGURATION AND OPERATING CONDITIONS USED SATISFY
THE ANALYTICAL REQUIREMENTS SET FORTH IN THIS METHOD AND TO
MAINTAIN QUALITY CONTROL DATA CONFIRMING INSTRUMENT PERFORMANCE
AND ANALYTICAL RESULTS.
The data must include hardcopies or computer readable storage
media which can be readily examined by an audit team. The data
oust demonstrate defendable choices of instrument operating
conditions which minimize interferences and optimize hydride
generation.
5. BBAffEPTS AND STANDARDS (SEE PART A)
S.I Fresh sodium borohydride solution (4.8% w/v in 0.25 N NaOH) must be
prepared daily from ACS reagent grade chemicals. The sodium
borohydride solution is essentially at saturation and will require
stirring with a magnetic stirrer during the analysis.
5.2 Potassium iodide solution (8% w/v) is prepared from ACS reagent grade
chemicals.
5.3 Calibration Standard Stock Solutions are prepared by dilution of the
stock standard solutions (See Part A) . The final solution must contain
all three elements at the same concentration in 50% HC1. The standard
stock solutions oust consist of antimony, arsenic, and selenium in
their lower oxidation states of plus five, plus five, and plus six
respectively.
5.3.1 The concentration of the elements required in the calibration
standard(s) will be dependent upon the instrumentation and so
the concentration used as well as the number of standards used
is left to the discretion of the analyst, although at least one
calibration standard and a calibration blank are required for
the calibration of the instrument.
5.4 Three types of blanks are required for ICP-Hydride analysis. The
calibration blank is used in establishing the calibration curve, the
preparation blank is used to monitor for possible contamination
resulting from the sample preparation procedure, and the rinse blank is
used to flush the system between all samples and standards.
5.4.1 The calibration blank solution and rinse blank both consist of
50% (v/v) HC1 in ASTM Type I water. Note:' As with all
digested samples, add an equal volume of concentrated HC1 to
the blank to give a 50% (v/v) HC1 analytical sample. This acid
must be from the same lot of HC1 as that used in preparation of
the standards.
5.4.2 The preparation blank*'fs prepared as specified in Exhibit E.
D-25 10/91
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Exhibit D Method 206.3
5.5 The continuing calibration verification standard final solution must.
contain all three elements at the same concentration in 50% (v/v) HC1.
5.6 Matrix matching, with the samples, is mandatory for all blanks,
standards, and quality control samples, to avoid inaccurate
concentration values due to possible standard curve deviations.
6. PROCgDORg
6.1 Set up the instrument with the proper operating parameters as
established in Section 4.1. The instrument must be allowed to become
thermally stable before beginning the analysis. This requires at least
30 minutes of operation with the plasma lit prior to calibration.
6.2 Initiate appropriate operating configuration of the computer.
6.3 Due to the diverse modifications of hydride manifolds, no detailed
operational instructions can be provided. Instead, the analyst should
consult the manufacturer instructions on which type of manifold would
be best utilized with their particular instrument.
6.4 The flow of the waste line from the phase separator returning to the
pump will need to be optimized for each particular system. This is
necessary to prevent sample carry-over and be checked and documented by
continuously analyzing a blank solution after a high (greater than 10
mg/L) standard for each element.
6.5 The appropriate cycle times for sampling and rinsing must be determined
for each system. These criteria are to be documented and reported in
accordance with Section E of this method. Direct monitoring of the
photocurrent from the detector system for one of the elements should be
conducted to establish when the signal is at steady state, both for the
sample response and in rinsing the sample from the system.
Alternatively, sequential exposures of about 5 to 10 seconds during a
cycle can establish the appropriate time intervals. Rinse tines of at
least 45 seconds are required between samples. It is required that the
contractor document these parameters quarterly in the form of raw data
results of this optimization. To test for sample carry-over, the
analyst must analyze a high standard (greater than 10 mg/L) containing
all the elements followed by the continuous aspiration for the blank
solution. The blank solution is to be continuously monitored (in
intensity units) until the intensity becomes stable at the background
level. The time required to completely remove all traces of any
element is the required wash time. If any sample solution analyzed
contains any element at a concentration greater than the high standard
solution analyzed above (prior to dilution correction), the sample
following that solution must be reanalyzed. Alternately, the wash
check above may be repeated and documented at a higher concentration
than the sample.
6.6 The use of a mass flow controller on the carrier argon flow is
recommended in place of a rotameter.
D-26 10/91
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Exhibit D Method 206.3
i
6.7 System Startup
6.7.1 All pump lines should be pumping only ASTM Type I water.
6.7.2 Place the sample pump line in the acid rinse solution. If
potassium iodide is being used with the hydride manifold, place
its sample line in the KI solution.
6.7.3 After the acid has entered the hydride manifold, start the
sodium borohydride flow. Just before the sodium borohydride
cones in contact with the rinse solutions, slow the pump down
to about half of its normal flow. As soon as the borohydride
cones in contact with the acid rinse, a violent reaction starts
that evolves hydrogen. Be ready to make adjustments to help
stabilize the plasma.
6.7.4 As the plasma stabilizes, slowly increase the flow of the pump
to the appropriate level, making adjustments to stabilize the
plasma as the amount of hydrogen increases. Hereafter, do not
let the sample line remain out of the rinse solution or a
sample too long. If the borohydride is allowed to build up in
the separator without constant acid introduction, the plasma
will be extinguished once acid is introduced. To stop the
analysis, place the borohydride line in water and continue
pumping the acid until hydrogen evolution ceases. As the
hydrogen evolution decreases, adjustments will be needed to
stabilize the plasma.
7. IOH AMP SAFr AHALTSIS
7.1 Calibrate the instrument using the appropriate matrix matched
calibration standard solution(s) . The calibration must include a
calibration blank and at least one standard.
7.2 All standard, blank, and sample solutions must contain 50% (v/v) HC1.
A change in the acid strength changes the slope of the calibration
curve and can cause inaccurate results. All digested samples must be
diluted 1:1 with concentrated HC1 to give a 50% (v/v) HC1 matrix in the
analytical sample. The samples are then ready for analysis.
7.3 All standard, blank, and sample solutions must be heated at 90-100°C
for a minimum of 10 minutes before being introduced into the hydride
manifold. In order to ensure that sufficient heat is being applied,
the results of two portions of the standards that were heated to a
different extent (e.g., one for 10 minutes versus one for 15 minutes)
must be compared. If the result yields a difference of more than 5%,
the heating time must be increased until a difference of 5% or less is
obtained. All standards, blanks, and sample solutions must be analyzed
after being heated for the length of time that yields a 5% difference
or less .
D-27
10/91
-------
Exhibit D Method 206.3
*
7.4 In order to determine if the sample result is to be calculated by the
Method of Standard Addition (MSA), an analytical spike must be
performed and analyzed immediately after each sample analysis. The
analytical spike recovery must be used to determine the need for MSA as
explained in Exhibit E. The spiking solution volume must not exceed
10% of the sample volume. The diluent should be 50% (v/v) HC1 in the
ASTM Type 1 water.
7.5 If MSA is required, follow the procedure given in Exhibit E.
7.6 Dilute and reanalyze samples that are more concentrated than the linear
range for an analyte.
8. CALCULATIONS
8.1 Calculate sample concentrations in (ug/L) by multiplying the analytical
concentration by the appropriate dilution factors used.
8.2 Appropriate concentration units must be specified on the required
forms. The quantitative values shall be reported in units of
micrograms per liter (ug/L) for aqueous samples, NO other units are
acceptable.
9.
9.1 Quality Control must be performed as specified in Exhibit E.
9.2 All quality control (QC) data must be submitted with each data package
as specified in Exhibit B.
D-28 10/91
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Exhibit D Methods 202.2 and 202.1
PART D
GRAPHITE FURNACE AhD FLAME ATOMIC ABSORPTION SPECTROSCOFT METHOD
1. SCOPE AND APPLICATION
1.1 Graphite furnace atomic absorption procedures are provided to achieve
the necessary sensitivity and detection limits needed for the analysis
of drinking and ground/well water.
1.2 Detection limits, sensitivity, and opi' •* ranges of the metals will
vary with the various makes and models o; satisfactory graphite furnace
atomic absorption spectrophotometers.
1.3 Because of the difference between various makes and models of
satisfactory instruments, no detailed instrumental operating
instructions can be provided. Instead, the analyst is referred to the
instructions provided by the manufacturer of Chat instrument.
2. SUMMARY OF METHOD
2.1 Using Che furnace technique in conjunction with an atomic absorption
spectrophotometer, a representative aliquot of a sample is placed in a
graphite cube in the furnace, evaporated to dryness, charred, and
atomized. Radiation from a given exciCed element is passed through the
vapor containing ground state atoms of that elemenc. The intensity of
Che transmicced radiation decreases in proportion to the amount of the
ground state element in Che vapor. The metal atoms Co be measured are
placed in Che beam of radiation by increasing Che temperature of the
furnace thereby causing Che injected specimen Co be volatilized. A
monochromator isolates the characteristic radiation from Che hollow
cathode lamp and a photosensitive device measures Che attenuated
transmitted radiation.
3.
3.1 The composition of the sample matrix can have a major effect on Che
analysis. By modifying Che sample matrix, eicher to remove
interferences or to stabilize the analyte, interferences can be
minimized. Examples are the addition of ammonium nitrate to remove
alkali chlorides and the addition of ammonium phosphate to retain
cadmium.
3.2 Gases generated in the furnace during atomization may have molecular
absorption bands encompassing the analytical wavelength. Therefore the
use of background correction is required for all furnace analysis.
3.3 Continuum background correction cannot correct for all types of
background interference. When the background interference cannot be
compensated for, choose an alternate wavelength, chemically separate
Che analyte from the interferent, or use an alternate form of
background correction, e.g., Zeeman background correction.
D-29 10/91
-------
Exhibit D Methods 202.2 and 202.1
3.4 Interferences from a smoke producing sample matrix can sometimes be
reduced by extending the charring time at a higher temperature or
utilizing an ashing cycle in the presence of air. Care must be taken
to prevent loss of analyte.
4. APPARATUS
4.1 Atomic absorption spectrophotometer. Single or dual channel, single or
double beam instrument having a grating monochromator, photonultiplier
detector, adjustable slits, a wavelength range of 190 to 800 not,
background correction, and provisions for interfacing with a recording
device.
4.2 Graphite furnace. Any furnace device capable of reaching the specified
temperatures is satisfactory.
i
4.3 Operational Requirements
4.3.1 System configurations - - Because of the differences between
various makes and models of satisfactory instruments, no
detailed operating instructions can be provided. Instead, the
analyst should follow the instructions provided by the
manufacturer of the particular instrument. Sensitivity,
instrumental detection limit, precision, linear dynamic range
and interference effects must be investigated and established
for each individual analyte on that particular instrument.
IT IS THE RESPONSIBILITY OF THE AHALTST TO VERIFY THAT THE
INSTRUMENT CONFIGURATION AND OPERATING CONDITIONS USED SATISFY
THE ANALYTICAL REQUIREMENTS SET FORTH IN THIS METHOD AND TO
MAINTAIN QUALITY CONTROL DATA CONFIRMING INSTRUMENT PERFORMANCE
AND ANALYTICAL RESULTS.
The data must include hardcopies or. computer readable storage
media which can be readily examined by an audit team. The data
must demonstrate defendable choices of furnace temperature
program and matrix modifiers.
5. "fiA/rETTS AND STANDARDS (SEE PART A)
5.1 Matrix matching, with the samples, is mandatory for all blanks,
standards, and quality control samples, to avoid inaccurate
concentration values due to possible standard curve deviations.
5.2 Preparation of standards. Calibration standards are prepared by
diluting stock metal solutions at the time of analysis and are
discarded after use. Prepare at least three calibration standards in
graduated amounts in the appropriate range by combining an appropriate
volume of stock solution in a volumetric flask. Add 2 mL of (1+1) HN03
and dilute to 100 mL with ASTM Type I water. The calibration standards
must be prepared using the same type of acid or combination of acids at
the same concentration.
D-30 10/91
-------
Exhibit D Methods 202.2 and 202.1
•«*
5.3 Two types of blanks are required for GFAA analysis; the calibration
blank is used in establishing the analytical curve while the
preparation blank is used to correct for possible contamination
resulting from various acids used in the sample processing.
The calibration blank is prepared by diluting 2 mL of (1+1) fflK>3 to 100
mL with ASTM Type I water. The preparation blank is' prepared as
specified in Exhibit E.
6 .
6.1 Set up instrument with proper operating parameters established by the
instrument manufacturer. The individual steps; drying, thermal
pretreatment, and atomization require careful consideration to ensure
each process is carried out effectively. The instrument oust be allowed
to become thermally stable before beginning. This usually requires at
least 30 min. of operation prior to calibration. Background correction
must be used.
6.2 Calibration and Sample Analysis
6.2.1 Calibrate instrument according to instrument manufacturer's
recommended procedures, using calibration standard solutions.
Beginning with the calibration blank and working towards the
highest standard, run at least three standards and calibrate.
6.2.2 In order to determine if the sample result is to be calculated
by MSA, an analytical spike must be performed and analyzed
after each sample analysis. The analytical spike recovery must
be used to determine the need for MSA as explained in Exhibit
E. The spiking solution volume must not exceed 10% of the
sample volume.
6.3 If method of standard addition is required, follow the procedure given
in Exhibit E.
6.4 Dilute and reanalyze samples that are more concentrated than the linear
range for an analyte.
7. CALCULATIOHS
7.1 If dilutions were performed, the appropriate factor mist be applied to
sample values.
7.2 Appropriate concentration units must be specified on the required
forms. The quantitative values shall be reported in units of
micro grams per liter (ug/L) for aqueous samples, NO other units are
acceptable.
D-31 10/91
-------
Exhibit D Methods 202.2 and 202.1
8. FLAME AA
8.1 Calciua (Method 215.1 CLP-M* Atonic Absorption, Plane Technique)
Optimum Concentration Range: 0.2-7 ng/L using a wavelength of 422.7 mn
Sensitivity: 0.08 ng/L
Detection Limit: 0.01 ng/L
Preparation of S7?n^grd Solution
1. Stock Solution: Suspend 1.250 g of 0*0)3 (analytical reagent grade),
dried at 180°C for 1 hour before weighing, in de ionized distilled water
and dissolve cautiously with a nininun of dilute HCL. Dilute to 1000 nL
with deionized distilled water. 1 nL - 0.5 ng Ca (500 ng/L).
2. Lanthanum chloride solution: Dissolve 29 g of La2^3t slowly and in
small portions, in 250 nL cone. HC1 (Caution: Reaction is violent) and
dilute to 500 nL with deionized distilled water.
3. Prepare dilutions of the stock calciun solutions to be used as
calibration standards at the tine of analysis. To each 10 nL of
calibration standard and sample alike add 1.0 nL of the lanthanum
chloride solution, i.e., 20 nL of standard or sample + 2 nL LaCl3 - 22
nL.
1. Calcium hollow cathode lamp
2. Wavelength: 422.7 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Reducing
Notes
1. Phosphate, sulfate and aluminum interfere but are nasked by the addition
of lanthanum. Because low calcium values result if the pH of the sample
is above 7, both standards and samples are prepared in dilute
hydrochloric acid solution. Concentrations of magnesium greater than
1000 ng/L also cause low calciun values . Concentrations of up to 500
ng/L each of sodium, potassiun and nitrate cause no interference.
2. Anionic chemical interferences can be expected if lanthanum is not used
in samples and standards.
3. The nitrous oxide-acetylene flame will provide two to five tines greater
sensitivity and freedon from chenical interferences. lonization
interferences should be controlled by adding a large amount of alkali to
the sample and standards. The analysis appears to be free from chemical
suppressions in the nitrous oxide -acetylene flame. C Atomic Absorption
Newsletter 14, 29 [1975]).
4. The 239.9 nm line may also be used. This line has a relative
sensitivity of 120.
CLP-M modified for the Contract Laboratory Program.
D-32 10/91
-------
Exhibit D Methods 202.2 and 202.1
•t
8.2 Magnesium (Method 242.1 CLP-M* Atomic Absorption, Plane Technique)
Optimum Concentration Range: 0.02-0.5 mg/L using a wavelength of 285.2 nm
Sensitivity: 0.007 mg/L
Detection Limit: 0.001 mg/L
Preparation of Stan*Mrd Solution
1. Stock Solution: Dissolve 0.829 g of magnesium oxide, MgO (analytical
reagent grade), in 10 mL of redistilled HN03 and dilute to 1 liter with
deionized distilled water. 1 mL - 0.50 mg Mg (500 mg/L).
2. Lanthanum chloride solution: Dissolve 29 g of La2°3> slowly and in
small portions in 250 mL concentrated HC1 (Caution: Reaction is
violent), and dilute to 500 mL with deionized distilled water.
3. Prepare dilutions of the stock magnesium solution to be used as
calibration standards at the time of analysis. To each 10 mL volume of
calibration standard and sample alike add 1.0 mL of the lanthanum
chloride solution, i.e., 20 mL of standard or sample +• 2 mL LaCl3 - 22
mL.
Xnstir1 in|ftntal Pffr^iweters (General)
1. Magnesium hollow cathode lamp
2. Wavelength: 285.2 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. The interference caused by aluminum at concentrations greater than 2
mg/L is masked by addition of lanthanum. Sodium, potassium and calcium
cause no interference at concentrations less than 400 mg/L.
2. The following line may also be used: 202.5 nm Relative Sensitivity 25.
3. To cover the range of magnesium values normally observed in surface
waters (0.1-20 mg/L), it is suggested that either the 202.5 nm line be
used or the burner head be rotated. A 90° rotation of the burner head
will produce approximately one-eighth the normal sensitivity.
*CLP-M modified for the Contract Laboratory Program.
D-33 10/91
-------
; Exhibit D Methods 202.2 and 202.1
8.3 Potassium (Method 258.1 CLP-M Atonic Absorption, Plane Technique)
Optimum Concentration Range: 0.1-2 mg/L using a wavelength of 766.5 no
Sensitivity: 0.04 mg/L
Detectioji Limit: 0.01 mg/L
of Standard Solution
1. Stock Solution: Dissolve 0.1907 g of KC1 (analytical reagent grade),
dried at 11&1°C, in de ionized distilled water and make up to 1 liter. 1
mL - 0.10 mg 1 (1.00 mg/L).
2. Prepare dilution- if the stock solution to be used as calibration
standards at the tlae of analysis. The calibration standards should be
prepared using the same type of acid and at the same concentration as
will result in Che sample to be analyzed either directly or after
processing.
Instrumental Parflmftyrs (General )
1. Potassium hollow cathode lamp
2. Wavelength: 766.5 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Slightly oxidizing
Notes
1. In air-acetylene or other high temperature flames (>2800°C) , potassium
can experience partial ionization which indirectly affects absorption
sensitivity. The presence of other alkali salts in the sample can
reduce this ionization and thereby enhance analytical results. The
ionization suppress ive effect of sodium is small if the ratio of Na to K
is under 10. Any enhancement due to sodium can be stabilized by adding
excess sodium (1000 ug/mL) to both sample and standard solutions. If
•ore stringent control of ionization is required, the addition of cesium
should be considered. Reagent blanks muse be analyzed to correct for
potassium impurities in the buffer zone.
2. The 404.4 nm line may also be used. This line has a relative
sensitivity of 500.
3. To cover the range of potassium values normally observed in surface
waters (0.1-20 mg/L), ic is suggested that the burner head be rotated. A
90° rotation of the burner head provides approximately one -eighth the
normal sensitivity.
CLP-M modified for the Contract Laboratory Program.
D-34 10/91
-------
Exhibit D Methods 202.2 and ,202.1
8.4 Sodium (Method 273.1 CLP-M Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.03-1 mg/L using a wavelength of 589.6 TUB
Sensitivity: 0.015 mg/L
Detection Limit: 0.002 mg/L
Preparation of Standard Solutions
1. Scock Solution: Dissolve 2.542 g of NaCl (analytical reagent grade),
dried at 140°C, in de ionized distilled water and make up to 1 liter. 1
mL - 1 mg Na (1000 mg/L) .
2. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. The calibration standards should be
prepared using the same type of acid and at the same concentration as
will result in the sample to be analyzed either directly or after
processing.
Parameters (genera;)
1. Sodium hollow cathode lamp
2. Wavelength: 589.6 nm
3. Fuel: Acetylene
4 . Oxidant : Air
5. Type of flame: Oxidizing
Notes
1. The 330.2 nm resonance line of sodium, which has a relative sensitivity
of 185, provides a convenient way to avoid the need to dilute more
concentrated solutions of sodium.
2. Low- temperature flames increase sensitivity by reducing the extent of
ionization of this easily ionized metal, lonization may also be
controlled by adding potassium (1000 mg/L) to both standards and
samples .
9. Q?^LrTT COHTROL
9.1 Quality control must be performed as specified in Exhibit E.
9 . 2 All quality control (QC) data must be submitted with each data package
as specified in Exhibit B.
CLP-M modified for the Contract Laboratory Program.
D-35 ILC02.0
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Exhibit D Metpd 200.10
PART E
INDUCTIVELY COUPLED PLASMA - MASS SPECTROMETRY
1. SCOPE AMD APPLICATION
1.1 Metals for which this method is applicable are listed in Table II,
Exhibit C in low concentration water samples. Instrument detection
limits, sensitivities, and linear ranges for these elements will vary
with the matrices, instrumentation, and operating conditions. Use of
this method is restricted to spectroscopists who are knowledgeable in
the recognition and the correction of spectral, chemical, and physical
interferences in ICP-MS. Experience requirement is 1 year on a
commercially available IGF-MS.
2.
CTTMMADV nv
2.1 The method describes the multi-elemental determination of analytes by
ICP-MS. The method measures ions produced by a radio-frequency
inductively coupled plasma. Analyte species originating in a liquid
are nebulized and the resulting aerosol transported by argon gas into
the plasma torch. The ions produced are entrained in the plasma gas
and by means of a water cooled interface, introduced into a quadrupole
mass spectrometer, capable of providing a. resolution better than or
equal to 1 amu peak width at 10% of the peak height. The water-cooled
interface consisting of tandem skimmers, is differentially pumped and
leads into the high vacuum chamber of the mass spectrometer. The ions
and ion clusters produced in the plasma and those formed during the
introduction of the ion beam into the mass spectrometer, are sorted
according to their mass-to-charge ratios and quantified with a channel
electron multiplier. Interferences must be assessed and valid
corrections applied or the data flagged to indicate problems. Use of
the internal standard technique is required to compensate for
suppressions and enhancements caused by sample matrices.
3.
3.1 laobaric elemental Interferences in ICP-MS are caused by isotopes of
different elements forming ions with the same nominal mass-to-charge
ratio (m/z). Table XIII, Exhibit C, shows isobaric interferences and
the secondary masses which would be analyzed to correct for these
interferences. A data system must be used to correct for these
interferences. This involves determining the signal for another
isotope of the interfering element and subtracting out the appropriate
signal from the isotope of interest. Data that is corrected must be
noted in the report along with the exact calculations used. Commercial
ICP-MS instruments nominally provide unit resolution at 10% of the peak
height, and very high ion currents at adjacent masses can contribute to
ion signals at the mass of interest. Table XII, Exhibit C, shows
approximate concentrations at which adjacent masses give rise to a
contribution of 10 ug/L to the analyte of interest at a resolution of 1
amu at 10% peak height, if the mass were chosen for quantitation. It
should be noted that the information described in Table XII, Exhibit C,
was experimentally derived and the interferences which are described
D-36 10/91
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Exhibit D Method 200.10
occur fron several different sources. One interference is the effect
of resolution on adjacent peaks. This has a larger effect at 1 amu
less Chan the interferent than at 1 amu greater than the interferent' s
mass due to the trapezoidal peak shape associated with a quadrupole
mass spectrometer. Another interference which would be observed is the
formation of a hydride ion. These interferences only cause an
interference at 1 ami greater than the interf erent's na*s. It should
also be remembered that these interferences are not necessarily linear
and attempts should not be made to extrapolate the values to a
particular data set. The table has been included for its informational
content alone.
3.2 Isobarie molecular and doubly charged ion interferences in ICP-MS are
caused by ions consisting of more than one atom or charge. Table XIII,
Exhibit C, lists isobaric molecular-ion interferences which could
affect the analytes. It should be noted that many of these
interferences are extremely rare, but adverse effects on data quality
could occur if the individual constituents occurred in the sample at
sufficiently high concentrations. When the interferences cannot be
avoided by the use of another isotope with sufficient natural
abundance, corrections to the data must be applied. Corrections for
molecular-ion interferences may either be based upon the natural
isotope ratios of the molecular ion or a determination of the actual
amount of interference which occurs when the interferant is present.
If a correction for an oxide ion is used, the correction may be
normalized to the extent of oxide formation of an appropriate internal
standard previously demonstrated to form the same level of oxide as the
interf erant. This second type of correction has been reported for
oxide ion corrections using ThO/Th for use on rare earth elements.
Most isobaric interferences that could affect ICF-MS determinations
have been identified in the literature.
3.3 Physical interferences are effects associated with the sample
nebulization and transport processes as well as ion-transmission
efficiencies. Nebulization and transport processes are those in which
the matrix component causes a change in surface tension or viscosity in
a manner different from the standards used in performing calibration.
Internal standards have been used to correct for these interferences.
The interferences are primarily suppressions and are seen by the
lighter elements more than the heavier elements. The effects are
greater for matrix components with heavier atomic mass than for matrix
components with lighter atomic mass. Changes in matrix composition
therefore can cause significant suppressions and enhancements.
Dissolved-solid levels can contribute deposits on the nebulizer tip of
a pneumatic nebulizer and on the interface skimmers (reducing the
orifice size and the instrument performance) . Total solid levels below
0.2% (2,000 ppm) have been recommended to minimize solid deposition.
Internal standards must be affected to the same degree as the analyte
to demonstrate that they compensate for these interferences. A minimum
of three internal standards, listed in Table X Exhibit C, bracketing
the mass range, must be used. When the intensity level of an internal
standard is less Chan 30% or greater than 125% of the intensity of the
first standard used duiirg calibration, the sample must be reanalyzed
D-37 10/91
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Exhibit D HeChod 200.10
after performing a fivefold (1+4) dilution. The intensity levels of
the internal standards for the Continuing Calibration Blank and
Continuing Calibration Verification Solution oust agree within ±20
percent of the intensity level of the internal standard of the Initial
calibration blank solution. If they do not agree, terainate the
analysis, correct the problem, recalibrate, and reanalyze the previous
10 samples at no additional cost.
3.4 Memory interferences are effects which are dependant upon the relative
concentration differences between samples or standards which are
analyzed sequentially. Sample deposition on the sampler and skimmer
cones, spray chamber design, and the type of nebulizer used, affect the
extent of the memory interferences which are present. To verify that
memory effects do not have an adverse impact on data quality, the
memory test must be performed on the tuned and calibrated instrument
before any analyses are performed. A multielement memory test solution
containing levels of analytes as specified in Table IX, Exhibit C, is
aspirated into the system for a normal sample exposure period. A blank
solution is then introduced, noting the time when the uptake tube is
switched to the blank solution. After the normal routine rinse time
has elapsed, begin a routine analysis of the blank solution. Inspect
the resulting data Co see if any analytes are in excess of the IDL. If
there are, reanalyze the blank to eliminate the possibility of actual
blank contamination. A decreased value on the second analysis
indicates a memory problem rather than blank contamination. If a
memory problem does exist (see Exhibit E) for a given analyte, increase
the rinse time until the system passes die memory test. If the
increased rinse time is not feasible from a sample throughput
standpoint, a hardware change may be necessary.
4. ^fT^WfOS AND
4.1 Inductively coupled plasma - mass spectrometer:
4.1.1 System capable of 1 amu resolution from 6 -253 amu with a data
system that allows corrections for isobaric interferences and
the application of the internal standard technique. Use of a
mass -flow controller for the nebulizer argon and a peristaltic
pump for the sample solution are recommended.
4.1.2 Argon gas supply: high-purity grade (99.99%)
4 . 2 Operational Requirements
4.2.1 System Configuration -- Because of the differences between
various makes and models of satisfactory instruments, no
detailed operating instruction can be provided. Instead, the
analyst should follow the instructions provided by the
manufacturer of the particular instrument. Sensitivity,
instrumental detection limits (IDL's), precision, linear
dynamic range and interference effects must be established for
each analyte on a particular instrument. All reported
D-38 10/91
-------
Exhibit 0 Method 200.10
•**
measurements must be within the instrumental linear ranges.
The analyst must maintain quality control data confirming
instrument performance and analytical results.
IT IS THE RESPONSIBILITY OF THE ANALYST TO VERIFY THAT THE
INSTRUMENT CONFIGURATION AMD OPERATING CONDITIONS USED SATISFY
THE ANALYTICAL REQUIREMENTS SET FORTH IN THIS METHOD AND TO
MAINTAIN QUALITY CONTROL DATA CONFIRMING INSTRUMENT PERFORMANCE
AND ANALYTICAL RESULTS.
The data must include hardcopies and computer readable storage
media which can be readily examined by an audit team. The data
must demonstrate defendable choices of instrument operating
conditions which minimize interferences such as oxides.
4.3 Precautions must be taken to protect the channel electron multiplier
from high ion currents. The channel electron multiplier suffers from
fatigue after being exposed to high ion currents. This fatigue can
last from several seconds to hours depending on the extent of exposure.
During this time period, response factors are constantly changing which
invalidates the calibration curve, causes instability, and invalidates
sample analyses. Samples run during such periods are required reruns
at no additional cost.
4.4 Sensitivity, Instrument Detection Limits (IDL's), precision, linear
dynamic range, and interference effects must be established for each
analyte on a particular instrument. These parameters must be
determined for each configuration used if an instrument is equipped
with dual detector hardware. All reported measurements must be within
the instrumental linear dynamic ranges. All reported measurements from
a less sensitive detector configuration must exceed five times Che
documented instrumental detection limit for that detector
configuration. The analyst must maintain quality control data
confirming instrument performance and analytical results.
5 . MjA/fEffFS AND STANDARDS (SEE PART A)
5.1 Acids used in the preparation of standards and for sample processing
must be below the IDL's for the analytes of interest for the purpose of
a study. Redistilled acids or ultra-pure acids are required for use
with ICP-MS because of the high sensitivity of ICP-MS. Nitric acid at
less than 2 percent (v/v) is preferred for ICF-MS to minimize damage to
the interface and to minimize isobaric molecular -ion interferences with
the analytes. Many more molecular -ion interferences are observed on
the analytes when hydrochloric and sulfuric acids are used, as
demonstrated in Table XIII, Exhibit C. Concentrations of antimony and
silver above 300 ug/L require 1% (v/v) HC1 for stability.
5.2 Internal standards must be used to monitor and correct for changes that
occur from differences between standards and samples. This information
must be clearly reported in the raw data. The changes for which
internal standards correct are primarily physical interferences.
Internal standards must be present in all standards and samples at
identical levels by mixing the internal standard to the solution being
D-39 10/91
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Exhibit D Method 200.10
*
nebulized prior to the nebulizer. This may be accomplished by using a
second channel of the peristaltic pump to add the internal standard to
the uptake tube. If adding the solution to the uptake tube is not used
then the internal standard must be added in two separate aliquots to
the samples and standards to prevent the possibility of improperly
spiking the internal standard levels. The double spiking ensures that
misquantitation will not occur based upon a single internal standard
spike. Double spiking may occur either by adding a constant volume of
internal standard concentrate to identical volumes of the standards and
prepared samples, or by diluting the internal standard to the
appropriate level for its use in the analyses. One typical example is
to measure out 10.0 mL of all standards and samples into individual
containers, then 0.100 mL of a 10 mg/L solution of the internal
standard is added to each of the containers. This adds identical
amounts of the internal standard to each solution for analysis. The
concentrations of the analyte levels in the standards do not have to be
corrected for the dilution which occurs because the dilution is
canceled out when corrections to the samples are made for their
dilution.
5.2.1 Bismuth internal standard solution, stock, 1 mL - 100 ug Bi:
Dissolve 0.1115 g Bi203 in a minimum amount of dilute HNO3.
Add 10 mL cone. HNO3 and dilute to 1,000 mL with ASTM Type I
water.
5.2.2 Holmium internal standard solution, stock, 1 mL - 100 ug Ho:
Dissolve 0.1757 g Ho2(C03)2-5H20) in 10 mL ASTM Type I water
and 10 mL HNO3. After dissolution is complete, warm the
solution to degas. Add 10 mL cone. HNO3 and dilute to 1,000 mL
with ASTM Type I water.
5.2.3 Indium internal standard solution, stock, 1 mL - 100 ug In:
Dissolve 0.1000 g indium metal in 10 mL cone. HNO3. Dilute to
1,000 mL with ASTM Type 1 water.
5.2.4 Lithium internal standard solution, stock, 1 mL - 100 ug 6 LI:
Dissolve 0.6312 g 95 atom % enriched 6Li, U2C03 in 10 ml of
ASTM Type 1 water and 10 mL HN03. After dissolution is.
complete, warm the solution to degas. Add 10 mL cone. HNC>3 and
dilute to 1,000 mL with ASTM Type I water.
5.2.5 Molybdenum solution, stock, 1 mL - 100 ug Mo: Dissolve 0.2043
g (NH4>2MoO4 in ASTM Type I water. Dilute to 1,000 mL with
ASTM Type I water.
5.2.6 Rhodium internal standard solution, stock, 1 mL - 100 ug Rh:
Dissolve 0.3593 g ammonium hexachlororhodate (III) (NH^RhClg
in 10 mL ASTM Type I water. Add 100 mL cone. HC1 and dilute to
1,000 mL with ASTM Type I water.
5.2.7 Scandium internal standard solution, stock, 1 mL - 10O ug Sc:
Dissolve 0.15343 g Sc203 in 10 mL (1+1) hot HN03. Add 5 ml
cone. HN03 and dilute to 1,000 mL with ASTM Type I water.
D-40 10/91
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Exhibit D Method 200.10
*
5.2.8 Titanium solution, stock. J mL - 100 ug Ti: Dissolve 0.4133 g
(NH4)2TiF6 in ASTM Type I water. Add 2 drops of cone. HF and
dilute to 1.000 mL with ASTH Type I water.
5.2.9 Terbium internal standard solution, stock, 1 mL - 100 ug Tb:
Dissolve 0.1828 g Tb2(C03)3-5H20 in 10 mL (1+1) HN03. After
dissolution is complete, warm the solution to degas. Add 5 ml
cone. HNO3 and dilute to 1,000 mL with ASTM Type I water.
5.2.10 Yttrium internal standard solution, stock, \ mL - 100 ug Y:
Dissolve 0.2316 g Y2(C03)3' 3H20 in 10 mL (1+iZ/ h»03. Add 5 ml
cone. HNO3 and dilute to 1,000 mL with ASTM Type I water.
5.3 Mixed calibration standard solutions -- Dilute the stock-standard
solutions to levels in the linear range for the instrument in a solvent
consisting of 1 percent (v/v) HN03 in ASTM Type I water along with the
selected concentration of internal standards such that there is an
appropriate internal standard element for each of the analytes (see
Table X, Exhibit C). Prior to preparing the mixed standards, each
stock solution must be analyzed separately to determine possible
spectral interferences or the presence of impurities. Care must be
taken when preparing the mixed standards that the elements are
compatible and stable. Transfer the mixed standard solutions to
freshly acid-cleaned not previously used FEP fluorocarbon bottles for
storage. Fresh mixed standards must be prepared as needed with the
realization that concentrations can change on aging. Calibration
standards must be initially verified using a quality control sample and
monitored weekly for stability. Although not specifically required,
some typical calibration standard combinations follow.
5.3.1 Mixed standard solution I -- Manganese, beryllium, cadmium,
lead, silver, barium, copper, cobalt, nickel and zinc.
5.3.2 Mixed standard solution II - Arsenic, chromium, thallium, and
aluminum.
5.3.3 Mixed standard solution III -- Antimony, vanadium, iron.
5.3.4 Mixed standard solution IV -- Bismuth, holmium, indium,
scandium, yttrium, and terbium.
5.3.5 Mixed standard solution V -- Rhodium.
Note: If the addition of silver to the recommended acid
combination results in an initial precipitation, add
15 mL of ASTM Type I water and warm the flask until
the solution clears. Cool and dilute to 100 mL with
ASTM Type I water. For this acid combination the
silver concentration must be limited to 2 mg/L.
Silver under these conditions is stable in a tap water
matrix for 30 days.
D-41 10/91
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Exhibit 0 Method 200.10
5.4 Three types of blanks are required for the analysis. The calibration
blank is used in establishing and monitoring the calibration curve, the
preparation blank is used to monitor for (SO, ICB, CCB) possible
contamination resulting from the sample preparation procedure, and the
rinse blank is used to flush the system between all samples and
standards.
5.4.1 The calibration blank consists of 1 percent HN03 (v/v) in ASTM
Type I water along with the selected concentration of internal
standards such that there is an appropriate internal standard
element for each of the analytes (see Table X, Exhibit C) .
5.4.2 The preparation blank must contain all the reagents in the same
volumes as used ir. processing the samples. The preparation
blank must be carried through the complete procedure and
contain the same acid concentration in the final solution as
the sample solutions used for analysis (see Exhibit E).
5.4.3 The rinse blank consists of 2 percent ffiK>3 (v/v) in ASTM Type I
water. Prepare a sufficient quantity to flush the system
between standards and samples.
5.5 The Interference Check Solution(S) (ICS) is prepared to contain known
concentrations of interfering elements that will demonstrate the
magnitude of interferences and provide an adequate test of any
corrections. The ICS solution is 'detailed in Table V, Exhibit C. The
chloride concentration provides a means to evaluate software
corrections for chloride-related interferences such as ,C1 O"1" on 51v"*"
and 40Ar35Cl+ on 75As+. Since the natural abundance of 35C1 at 75.8
percent is 3.13 times the Cl abundance of 24.2 percent, the ion
corrections can be calculated with adjustments for isobaric
contributions. Iron is used to demonstrate adequate resolution of the
spectrometer on manganese. Molybdenum serves to indicate oxide effects
on cadmium isotopes. The other components are present to evaluate the
ability of the measurement scheme to correct for various molecular-ion
isobaric interferences. The ICS is used to verify that the
interference levels are corrected by the data system within quality
control limits.
5.5.1 Stock solutions for preparing ICS solutions A and AB may be
provided if available. Otherwise, refer to Table V, Exhibit C.
They must be diluted before use according to the instruction
provided. The prepared ICS solutions A and AB oust be prepared
weekly.
5.5.2 Mixed ICS solution I may be prepared by adding 13.903 g
Al(N03)3.9H20, 2.498 g CaC03 dried at 180'C for 1 h before
weighing, 1.000 g Fe, 1.658 g MgO, 2.305 g Na2C03, and 1.767 g
K2C03 to 25 mL
-------
Exhibit D MeChoa 2C.10
553 Mixed ICS solution II nay be prepared by slowly adding 7.M g
85% H3P04. 6.373 g 96% H2S04. 40.024 g 37% HC1, and 10.664 g
critic acid CgC^Hg to 100 mL of ASTM Type I water. Dilute to
1.000 mL wich ASTM Type I water.
5.5.4 Mixed ICS solution III nay be prepared by adding 5 oL each of
arsenic stock solution, chromium stock solution, copper stock
solution, and zinc stock solution, 10 mL each of cobalt stock
solution, nickel stock solution, and vanadium stock solution,
and 2.5 mL of cadmium stock solution. Dilute to 100 mL with 2%
HNO3.
5.5.5 ICS A may be prepared by adding 10 mL of mixed ICS solution I,
10 mL each of titanium stock solution, and molybdenum stock
solution, and 5 mL of mixed ICS solution II. Dilute to 100 mL
with ASTM Type I water. ICS solution A must be prepared fresh
weekly.
5.5.6 ICS AB may be prepared by adding 10 mL of mixed ICS solution I,
10 mL each of titanium stock solution and molybdenum stock
solution, 5 mL of mixed ICS solution II, and 2 mL of mixed ICS
solution III. Dilute to 100 mL with ASTM Type I water. ICS
solution AB must be prepared fresh weekly.
6. PROCEDURE
6.1 Initiate appropriate operating configuration of instrument computer.
6.2 Set up the instrument with the proper operating parameters. Allow at
least 30 minutes for the instrument to equilibrate before analyzing any
samples. This must be verified by running the tuning solution (Table
VII, Exhibit C) at least four times with relative standard deviations
of less than 10% for the analytes contained in the tuning solution.
6.3 Conduct mass calibration and resolution checks using the tuning
solution (100 ppb of the elements Li, Co, In, and Tl). The intensities
on die forms in Exhibit B (see Table VIII in Exhibit C) for the
response factor criteria are recommendations which might be helpful
when setting up the instruments but are not required criteria. The
mass calibration must meet the criteria specified in Table VIII,
Exhibit C, if mass calibration exceed those criteria then the mass
calibration must be adjusted to the correct values. The resolution
must also be verified to be less than 1.0 amu full width at 10 percent
peak height. To verify, the tuning solution must be analyzed at the
beginning and end of each 8 hour shift, and pass the tuning criteria.
6.4 Calibration and Sample Analysis
6.4.1 Calibrate the instrument for the analytes of interest using the
calibration blank and at least a single standard according to
the manufacturer's recommended procedure for each detector
configuration which will be used in analysis. Flush the system
with the rinse blank between each standard solution. Report
each integration during the calibration and sample analysis and
D-43 ILC02.0
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Exhibit D Method 200.10
use the average of the multiple integrations for both
standardization and saaple analysis. A minimum of two
replicate integrations are required for both calibration and
sample analysis. The raw data must include the concentrations
of elements in each integration as well as the average.
Additionally, If different detector configurations are used,
the raw data must indicate which detector configuration is
being used.
NOTE: Some elements (such as Hg, W, and Mo) require extended
flushing times which need to be determined for each
instrumental system. Run Memory Test on solution in Table IX,
Exhibit C, Co verify that memory problems will not affect the
data quality.
6.5 As a minimum, all masses which would affect data quality must be
monitored to determine potential effects from matrix components on the
analyte peaks. This information is to be used to assess data quality
and as a minimum must include the masses which are boldfaced and
underlined, listed in Table XIV, Exhibit C, for each element. These
masses must be monitored simultaneously in a separate scan or at the
time quantification occurs.
6.6 Flush the system with the rinse blank solution for a least 30 seconds
before the analysis of each sample. Aspirate each sample for at least
30 seconds before collecting data.
6 . 7 Dilute and reanalyze samples that are more concentrated than the linear
range for an analyte.
7. CALCULATIONS
7.1 If dilutions were performed, the appropriate corrections must be
applied to the sample values .
7.2 Appropriate concentration units must be specified on the required
forms. The quantitative values shall be reported in units of
micrograms per liter (ug/L) for aqueous samples. No other units are
acceptable .
8. qn^LJTY CONTROL
8.1 Quality control must be performed as specified in Exhibit E.
8.2 All quality control (QC) data must be submitted with each data package
as specified in Exhibit B.
8.3 To obtain analyte data of known quality, it is necessary to measure for
more than the analytes of interest in order to know the required
interference corrections. If the concentrations of interference
sources (such a C, Cl, Ho, Zr, W) are below the levels that show an
effect on the analyte level, uncorrected equations may be used provided
all QA criteria are met. It should be noted that monitoring the
interference sources does not necessarily require monitoring the
D-44 10/91
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Exhibit D Method 200.10
interference itself, but that a molecular species may be monitored to
indicate the presence of the interference. When corrected equations
are used all QA criteria must also be met. Extensive QC for
interference corrections are required at all times. The monitored
masses must include those elements whose oxygen, hydroxyl, chlorine,.
nitrogen, carbon and sulfur molecular ions which could impact the
analytes of interest. When an interference source is present, the
sample elements impacted must be flagged to indicate (a) the percentage
interference correction applied to the data or (b) an uncorrected
interference. The isotope proportions for an element or molecular-ion
cluster provide information useful for quality assurance. These tests
will enable the analyst to detect positive or negative interferences
that distort the accuracy of the reported values.
8.4 The interference check solution(s) (ICS) is prepared to contain known
concentrations of interfering elements that will demonstrate the
magnitude of interferences and provide an adequate test of any
corrections. The ICS is used to verify that the interference levels
are corrected by the data system within QC limits.
9. EZFERENCKS
9.1 G. Horlick et al.. Spectrochim. Acta 40B. 1555 (1985).
9.2 A. L. Gray. Spectrochim. Acta 40B, 1525 (1985); 41B, 151 (1986).
9.3 J. J. Thompson and R. W. Houk, Appl. Spectrosc. 41, 801 (1987).
9.4 J. W. McLaren et al., Anal. Chem. 57, 2907 (1985).
9.5 F. E. Kichte et al., Anal. Chem. 59, 1150 (1987).
9.6 S. H. Tan and G. Horlick. Appl. Spectrosc. 40, 445 (1986).
9.7 M. A. Vaughan and G. Horlick, Appl. Spectrosc. 40, 434 (1986).
9.8 D. Beauchemin et al. , Spectrochim. Acta 42B, 467 (1987).
9.9 R. S. Houk. Anal. Chem. 58, 97A (1986).
D-45 10/91
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Exhibit 0 Method 245.1
PART F
MERCURY ANALYSIS IN WATER
1. SCOPE AND APPLICATION
1.1 In addition to inorganic forms of mercury, organic mercurials nay also
be present. These organo-mercury compounds will not respond to the
cold vapor atonic absorption technique unless they are first broken
dovn and converted to mercuric ions. Potassium permanganate oxidizes
many of these compounds, but recent studies have shown that a number of
organic mercurials, including phenyl mercuric acetate and methyl
mercuric chloride, are only partially oxidized by this reagent.
Potassium persulfate has been found to give approximately 100% recovery
when used as the oxidant with these compounds. Therefore, a persulfate
oxidation step following the addition of the permanganate has been
included to insure that organo-mercury compounds, if present, will be
oxidized to the mercuric ion before measurement. A heat step is
required for methyl mercuric chloride when present in or spiked to a
natural system. For distilled water the heat step is not necessary.
1.2 The range of the method may be varied through instrument and/or
recorder expansion and sample size. Using a 100 mL sample, a detection
limit of 0.2 ug Hg/L can be achieved.
2. STMCART OP METHOD
2.1 The flame less AA procedure is a physical method based on the absorption
of radiation at 253.7 nm by mercury vapor. Organic mercury compounds
are oxidized and the mercury is reduced to the elemental state and
aerated from solution in a closed system. The mercury vapor passes
through a cell positioned in the light path of an atomic absorption
spectrophotometer. Absorbance (peak height) is measured as a function
of mercury concentration and recorded in the usual manner.
3.1 Possible interference from sulfide is eliminated by the addition of
potassium permanganate. Concentrations as high as 20 mg/1 of sulfide
as sodium sulfide do not interfere with the recovery of added inorganic
mercury from distilled water .
3.2 Copper has also been reported to interfere; however, copper
concentrations as high as 10 mg/L had no effect on recovery of mercury
from spiked samples.
3.4 While the possibility of absorption from certain organic substances
actually being present in the sample does exist, EMSL has not
encountered such samples. This is mentioned only to caution the
analyst of the possibility.
D-46 10/91
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Exhibit D Method 245.1
4. APPARATUS
4.1 Atomic Absorption Spectrophotometer: (See Note 1) Any atomic
absorption unit having an open sample presentation area in which to
mount the absorption cell is suitable. Instrument settings recommended
by the particular manufacturer should be followed.
NOTE 1: Instruments designed specifically for the measurement of
mercury using the cold vapor technique are commercially available and
may be substituted for the atomic absorption spectrophotometer.
IT IS THE RESPONSIBILITY OF THE ANALYST TO VERIFY THAT THE INSTRUMENT
CONFIGURATION AND OPERATION CONDITIONS USED SATISFY THE ANALYTICAL
REQUIREMENTS SET FORTH IN THIS METHOD AND TO MAINTAIN QUALITY CONTROL
DATA CONFIRMING INSTRUMENT PERFORMANCE AND ANALYTICAL RESULTS.
4.2 Mercury Hollow Cathode Lamp: Argon filled, or equivalent.
4.3 Recorder: Any multi-range variable speed recorder that is compatible
with the UV detection system is suitable.
4.4 Absorption Cell: Standard spectrophotometer cells 10 cm long, having
quartz end windows may be used.
4.5 Air Pump: Any peristaltic pump capable of delivering 1 liter of air
per minute may be used.
4.6 Flowmeter: Capable of measuring an air flow of 1 liter per minute.
4.7 Aeration Tubing: A straight glass fit having a coarse porosity.
Tubing is used for passage of the mercury vapor from the sample bottle
to the absorption cell and return.
4.8 Drying Tube: 6* X 3/4" diameter tube containing 20 g of magnesium
perchlorate. In place of the magnesium perchlorate drying tube, a
small reading lamp with 60V bulb may be used to prevent condensation of
moisture inside the cell. The lamp is positioned to shine on the
absorption cell maintaining the air temperature in the cell about 10*C
above ambient.
4.9 Autoanalyzer system (for automated spec crone trie method) including:
4.9.1 Sampler with provisions for sample mixing.
4.9.2 Proportioning pump.
4.9.3 Mercury manifold.
4.9.4 High temperature heating bath with two distillation coils.
4.9.5 Vapor-liquid separator
D-47 10/91
-------
Exhibit D Method 245.1
5. BiRA7SffTs AMP STANDARDS (SEE PART A)
5.1 Sulfuric Acid, Cone: Reagent grade.
5.1.1 Sulfuric acid, 0.5 N: Dilute 14.0 a" " cone, sulfuric acid to
1.0 liter with ASTM Type I w.£er.
5.1.2 Sulfuric acid, 2 N: Dilute 56 mL of cone, sulfuric acid to 1
liter with ASTM Type I water.
5.1.3 Sulfuric acid, 10%: Dilute 100 mL cone, sulfuric acid to 1
liter with ASTM Type I water.
5.2 Nitric Acid, Cone: Reagent grade of low mercury content.
5.2.1. Nitric Acid, 0.5% Wash Solution: Dilute 5 mL of concentrated
nitric acid to 1 liter with ASTM Type I water.
5.3 Stannous Sulfate (Stannous chloride may be used in place of stannous
sulfate.)
5.3.1 Manual method: Add 25 g stannous sulf ate to 250 mL of 0.5 N
sulfuric acid. This mixture is a suspension and should be
stirred continuously during use.
5.3.2 Automated method: Add 50 g stannous sulf ate to 500 mL of 2 N
sulfuric acid. This mixture is a suspension and should be
stirred continuously during use.
5.4 Sodium Chloride-Hyroxylamine Sulfate Solution (Hydroxylamine
hydrochloride may be used in place of hydroxylamine sulf ate.)
5.4.1 Manual method: Dissolve 12 g of sodium chloride and 12 g of
hydroxylamine sulfate in ASTM Type I water and dilute to 100
mL.
5.4.2 Automated method: Dissolve 30 g of sodium chloride and 30 g of
hydroxylamine sulfate in ASTM Type I water to 1 liter.
5.5 Potassium Permanganate
5.5.1 Manual method: 5% solution, w/v. Dissolve 5 g of potassium
permanganate in 100 mL of ASTM Type I water.
5.5.2 Automated method:
5.5.2.1 0.5% solution, w/v. Dissolve 5 g of potassium
permanganate in 1 liter of ASTM Type I water.
5.5.2.2 0.1 N. Dissolve 3.16 g of potassium permanganate in
ASTM Type I water and dilute to 1 liter.
D-48 10/91
-------
Exhibit D Method 245.1
5.6 Potassium Persulfate
5.6.1 Manual method: 5% solution, w/v. Dissolve 5 g of potassium
persulfate in 100 mL of ASTM Type I water.
5.6.2 Automated method: 0.5% solution, w/v. Dissolve 5 g potassium
persulfate in 1 liter of ASTM Type I water.
5.7 Working Mercury Solution: Make successive dilutions of the stock
mercury solution to obtain a working standard containing 0.1 ug per mL.
This working standard and the dilutions of the stock mercury solution
should be prepared fresh daily. Acidity of the working standard should
be maintained at 0.15% nitric acid. This acid should be added to the
flask as needed before the addition of the aliquot.
5.8 Air Scrubber Solution: Mix equal volumes of 0.1 N potassium
permanganate and 10% sulfuric acid.
6. FRflCZDORE
6.1 Matrix matching, with the samples, is mandatory for all blanks,
standards, and quality control samples to avoid inaccurate
concentration values due to possible standard curve deviations.
6.2 Manual Spectrometrie Determination
6.2.1 Calibration and Sample Analysis
6.2.1.1 Transfer 0, 0.5, 1.0, 5.0 and 10.0 mL aliquots of
the working mercury solution containing 0 to 1.0 ug
of mercury to a series of 300 mL BOD bottles. Add
enough ASTM Type 1 water to each bottle to make a
total volume of 100 mL. Mix thoroughly and add 5 mL
of cone, sulfuric acid and 2.5 mL of cone, nitric
acid to each bottle. Add 15 mL of KMn04 solution to
each bottle and allow to stand at least 15 minutes.
Add 8 mL of potassium persulfate to each bottle and
heat for 2 hours in a water bath maintained at 95'C.
Alternatively, cover the BOD bottles with foil and
heat in an autoclave for 15 minutes at 120* C and 15
Ibs. Cool and add 6 mL of sodium chloride-
hydroxylamine sulfate solution to reduce the excess
permanganate. When the solution has been
decolorized wait 30 seconds, add 5 mL of the
stannous sulfate solution and immediately attach the
bottle to the aeration apparatus forming a closed
system. At this point the sample is allowed to
stand quietly without manual agitation. The
circulating pump, which has previously been adjusted
to a rate of 1 liter per minute, is allowed to run
continuously (see Note 4). The absorbance will
increase and reach maximum within 30 seconds. As
soon as 'the recorder pen levels off, approximately 1
minute, open the bypass valve and continue the
D-49 10/91
-------
Exhibit O Method 245.1
aeration until the absorbance returns to its minimum
value (see Note 5). Close the bypass valve, remove
the stopper and frit from the BOO bottle and
continue the aeration. Proceed with the standards
and construct a standard curve by plotting peak
height versus aicrograas of mercury.
NOTE 4: An open system where the mercury vapor is
passed through the absorption cell only once may be
used instead of the closed system.
NOTE 5: Because of the toxic nature of mercury
vapor precaution must be taken to avoid its
inhalatitn. Therefore, a bypass has been included in
the system to either vent the mercury vapor into an
exhaust hood or pass the vapor through some
absorbing media, such as: a) equal volumes of 0.1 M
KHn04, and 10% H2SO4, or b) 0.25% iodine in a 3% a
KI solution. A specially treated charcoal that vill
adsorb mercury vapor is available.
6.2.2. Transfer 100 mL, or an aliquot diluted Co 100 mL, containing
not more than 1.0 ug of mercury, to a 300 mL BOD bottle. Add 5
•L of sulfuric acid and 2.5 mL of cone, nitric acid mixing
after each addition. Add 15 mL of potassium permanganate
solution to each sample bottle (see Note 6). Shake and add
additional portions of potassium permanganate solution, if
necessary, until the purple color persists for at least 15
minutes. Add 8 mL of potassium persulfate to each bottle and
heat for 2 hours in a water bath at 95*C.
NOTE 6: The same amount of KMnO^ added to the samples should
be present in standards and blanks.
Cool and add 6 mL of sodium chloride-hydraxylamine sulfate to
reduce the excess permanganate (see Note 7). Purge the head
space in the BOD bottle for at least 1 minute and add 5 mL of
Stannous Sulfate and immediately attach the bottle to the
aeration apparatus. Continue as described under Calibration.
NOTE 7: Add reductant in 6 oL increments until KMnO4 is
completely reduced.
6.3 Automated Spectroneeric Determination
6.3.1 Matrix matching, with che samples, is mandatory for all blanks,
standards, and quality control samples to avoid inaccurate
concentration values due to possible standard curve deviations.
6.3.2 Calibration and Sample Analysis
6.3.2.1 From the Working Mercury solution prepare standards
• 'containing O.'2,'0.5, 1.0, 2.0, 5.0, 10.0, 15.0 and
20.0 ug Hg/L.
D-50 10/91
-------
Exhibit D Method 245.1
6.3.2.2 Sec up manifold.
6.3.2.3 Feeding all the reagents through the system with
acid wash solution through the sample line, adjust
heating bath to 105* C. Pump reagents through the
system until a steady baseline is obtained.
6.3.2.4 Turn on atomic absorption spectrophotometer , adjust
instrument settings as recommended by the
manufacturer, align absorption cell in light path
for maximum transaittance and place heat lamp
directly over absorption cell.
6.3.2.5 Arrange working mercury standards from 0.0 to 20.0
ug Hg/L in sampler and start sampling. Complete
loading of sample tray with unknown samples.
6.3.2.6 Prepare standard curve by plotting peak height of
processed standards against concentration values.
6.3.2 Determine concentration of samples by comparing sample peak
height with standard curve.
6.3.3 After the analysis is complete put all lines except the
sulfuric acid line in distilled water to wash out system.
After flushing, wash out the sulfuric acid line. Also flush
the coils in the high temperature heating bath by pumping
stannous sulfate through the sample lines followed by distilled
water. This will prevent build-up of oxides of manganese.
7.1 Determine the peak height of the unknown from the chart and read the
mercury value from the standard curve.
7.2 Calculate the mercury concentration in the sample by the formula:
ug Hg in 1,000
ug Hg/L - aliquot x
volume of aliquot in mL
7.3 Report mercury concentrations as follows: Below 0.20 ug/L, 0.20 ug
between 0.20 and 10.0 ug/L, two significant figures; equal to or above
10.0 ug/L, three significant figures.
7.4 Appropriate concentration units must be specified on the required
forms. The quantitative values shall be reported in units of
micrograms per liter (ug/L) for aqueous samples, NO other units are
acceptable.
7.5 If dilutions were performed, the appropriate corrections must be
applied to the sample values.
D-51 10/91
-------
Exhibit D Method 245.1
COHTROL
8.1 Quality control must be perforaed as specified in Exhibit E.
8.2 All quality control (QC) data must be submitted with each data package
as specified in Exhibit B.
9.
1. "Interim Methods for the Sampling and Analysis of Priority 14th Edition,
p. 156 (1975).1972.
2. Analy. 2. p. 317 (1970). Annual Book of ASTM Standards, Part 31,
•Water", Standard
3. Brandenberger, H. and Bader, H.. "The Determination of D3223-73, p. 343
(1976).
4. Determining Mercury in Water", Technicon, Adv. in Auto. Environmental
Monitoring and Support Laboratory, Cincinnati, Goulden, P.D. and Afghan,
B.K. "An Automated Method for
5. Kopp, J.F., Longbottom, M.C. and Lobring, L.B. "Cold Vapor Mercury by
Flameless Atomic Absorption II, A Static Vapor Method for Determining
Mercury", AWWA, vol. 64, p. 20, Jan.
6. Method", Atomic Absorption Newsletter 7,53 (1968).Ohio, August 1977,
revised October 1980.Op. cit. (#1), Methods 245.1 or 245.2.Pollutants in
Sediments and Fish Tissue," USEPA,
7. Standard Methods for the Examination of Water and Wastewater
D-52 10/91
-------
Exhibit D Method 335.2
PART G
METHOD FOR TOTAL CYANIDE ANALYSIS IN HATER
1. SCOPE AND
1.1 This method is applicable to the determination of cyanide in low
concentration water samples.
1.2 The manual coloroaetric procedure is used for concentrations below 1
ag/L of cyanide and is sensitive to about 10 ug/L.
1.3 The working range of the semi-automated spectrophotoaetric method is 5
to 200 ug/L. Higher level samples must be diluted to fall within the
working range.
2. SUMMARY OF METHOD
2.1 The cyanide as hydrocyanic acid (HCN) is released froa cyanide
coaplexes by means of a reflux-distillation operation and absorbed in a
scrubber containing sodium hydroxide solution. The cyanide ion in the
absorbing solution is then determined by volumetric titracion or
coloriaetrically.
2.2 In the colorimetric measurement the cyanide is converted Co cyanogen
chloride, CNC1, by reaction with chloraaine-T at a pH less than 8 .
without hydrolyzing to the cyanate. After the reaction is complete,
color is formed on the addition of pyridine-pyrazolone or
pyridinebarbituric acid reagent. The absorbance is read at 620 na when
using pyridine-pyrazolone or 578 na for pyridine-barbituric acid. To
obtain colors of comparable intensity, it is essential to have the at
salt content in both the sample and the standards.
3.
3.1 Interferences are eliminated or reduced by using the distillation
procedure described in Procedure 6.1.
3.2 Sulfides adversely affect the colorimetric and titration procedures.
If a drop of the distillate on lead acetate test paper indicates the
presence of sulfides, treat 25 mL more of the sample than that required
for the cyanide determination with powdered cadmium carbonate. Yellow
cadmium sulfide precipitates if the saaple contains sulfide. Repeat
this operation until a drop of the treated saaple solution does not
darken the lead acetate test paper. Filter the solution through a dry
filter paper into a dry beaker, and from the filtrate measure the
saaple to be used for analysis. Avoid a large excess of cadmium
carbonate and a long contact tiae in order to minimize a loss by
complexation or occlusion of cyanide on the precipitated material.
3.3 The presence of surfactants may cause the sample to foaa during
refluxing. If this occurs, the addition of an agent such as Dow
Corning 544 antifoam agent will prevent the foam from collecting in the
D-53 10/91
-------
Exhibit D Method 335.2
condenser. Fatty acids will distill and form soaps under alkaline
titration conditions, making the end point almost impossible to detect.
When this occurs, one of the spectrophotometric methods should be used.
4. APPARATUS
4.1 Reflux distillation apparatus. The boiling flask should be of 1 liter
size with inlet tube and provision for condenser. The gas absorber may
be a Fisher-Hilligan scrubber.
4.2 Microburet, 5.0 mL (for titration)
4.3 Spec tropho tome ter suitable for measurements at 578 nm or 620 nm with a
1.0 cm cell or larger (for manual spectrophotometric method).
4.4 For automated spectrophotometric method:
4.4.1 Sampler
4.4.2 Pump
4.4.3 Cyanide Manifold
4.4.4 SCIC Colorimeter with 15 mm flowcells and 570 nm filters
4.4.5 Recorder
4.4.6 Data System (optional)
4.4.7 Glass or plastic tubes for the sampler
5 . BKAJipmTS AHD STAHDAi^PS
5.1 Matrix matching, with the samples, is mandatory for all blanks,
standards, and quality control samples to avoid inaccurate
concentration values due to possible standard curve deviations.
5.2 Distillation and Preparation Reagents
5.2.1 Sodium hydroxide solution, 1.25N: Dissolve 50 g of NaOH in
ASTM Type I water, and dilute to 1 liter with distilled water.
5.2.2 Cadmium carbonate: powdered
5.2.3 Ascorbic acid: crystals
5.2.4 Sulfuric acid: concentrated
5.2.5 Magnesium chloride solution: Weight 510 g of MgCl2.6H20 into a
1000 mL flask, dissolved and dilute to 1 liter with ASTM Type I
water.
D-54 10/91
-------
Exhibit D Method 135.2
5.3 Stock Standards and Titration Reagents
5.3.1 Stock cyanide solution: Dissolve 2.51 g of KCN and 2 g KOH in
1 liter of ASTM Type I water. Standardize with 0.0192 N AgNC>3.
5.3.2 Standard cyanide solution, intermediate: Dilute 50.0 mL of
stock (1 mL - 1 Bg CN) to 1000 mL with ASTM Type I water.
5.3.3 Standard cyanide solution: Prepare fresh daily by diluting
100.0 mL of intermediate cyanide solution tc 1000 nL with ASTM
Type I water and store in a glass stoppered bottle. 1 mL - 5.0
ug CM (5.0 «g/L)-
5.3.4 Sodium hydroxide solution, 0.25 N: Dissolve 10 g or NaOH in
ASTM Type I water and dilute to 1 liter.
5.4 Manual Spectrophotometric Reagents
5.4.1 Sodium dihydrogenphosphate, 1 M: Dissolve 138 g of NaH2PC>4.H20
in a liter of ASTM Type I water. Refrigerate this solution.
5.4.2 Chloramine-T solution: Dissolve 1.0 g of white, water soluble
chloramine-T in 100 mL of ASTM Type I water and refrigerate
until ready to use. Prepare fresh weakly.
5.4.3 Color Reagent-One of the following may be used:
5.4.3.1 Pyridine-barbituric acid reagent: Place 15 g of
barbituric acid in a 250 mL volumetric flask and add
Just enough ASTM Type I water to wash the sides of
the flask and wet the barbituric acid. Add 75 mL of
pyridine and mix. Add 15 mL of HC1 (sp gr 1.19),
mix, and cool to room temperature. Dilute to 250 mL
with ASTM Type I water and mix. This reagent is
stable for approximately six months if stored in a
cool, dark place.
5.4.3.2 Pyridine-pyrazolin-5-one solution:
5.4.3.2.1 3-Methyl-lphenyl-2-pyrazolin-5-one
reagent, saturated solution: Add 0.25 g
of 3-methyl-l-phenyl-2-pyrazolin-5-one
to 50 mL of ASTM Tpye I water, heat to
60"C with stirring. Cool to room
temperature.
5.4.3.2.2 3,3'Dimethyl-1,1'-diphenyl [4,4'-bi-2
pyrazolin]-5,5'dione (bispyrazolone):
Dissolve 0.01 g of bispyrazolone in 10
mL of pyridine.
5.4.3.2.3 Pour solution (5.4.3.2.1) through
nonacid-washed filter paper. Collect
• the filtrate. Through the same filter
D-55 10/91
-------
Exhibit D Method 335.2
paper pour solution (5.4.3.2.2)
collecting the filtrate in the saae
container as filtrate from (5.4.3.2.1).
Mix until the filtrates are
homogeneous. The mixed reagent
develops a pink color but this does not
affect the color production with
cyanide if used within 24 hours of
preparation.
5.5 Semi-Automated Spec trophotome trie Reagents
5.5.1 Chloramine-T solution: Dissolve 0.40 g of chloramine-T in ASTM
Type I water and dilute to 100 mL. Prepare fresh daily.
5.5.2 Phosphate buffer: Dissolve 138 g of N«H2PO4.H20 in ASTM Type I
water and dilute Co 1 liter. Add 0.5 mL of Brij-35 (available
from Technicon). Store at 4*C(+2*C).
5.5.3 Pyridine-barbituric acid solution: Transfer 15 g of barbituric
acid into a 1 liter volumetric flask. Add about 100 mL of ASTM
Type I water and swirl the flask. Add 74 mL of pyridine and
mix. Add 15 mL of concentrated HC1 and mix. Dilute to about
900 mL with ASTM Type I water and mix until the barbituric acid
is dissolved. Dilute to 1 liter with ASTM Type I water. Store
at 4*C(±2-C).
5.5.4 Sampler wash: Dissolve 10 g of NaOH in ASTM Type I water and
dilute to 1 liter.
6. PROCEDURE
6.1 Manual Spectrophotometric Determination (Option B)
6.1.1 Withdraw 50 mL or less of the solution from the flask and
transfer to a 100 mL volumetric flask. If less than 50 mL is
taken, dilute to 50 mL with 0.25 H sodium hydroxide solution.
Add 15.0 mL of sodium phosphate solution and mix.
6.1.1.1 Pyridine-barbituric acid method: Add 2 mL of
chloraaine-T and mix. After 1 to 2 minutes, add 5
mL of pyridine-barbituric acid solution and mix.
Dilute to mark with ASTM Type I water and mix again.
Allow 8 minutes for color development then read
absorbance at 578 nm in a 1 cm cell within 15
minutes.
6.1.1.2 Pyridine-pyrazolone method: Add 0.5 mL of
chloramine-T and mix. After 1 to 2 minutes, add 5
mL of pyridine-pyrazolone solution and mix. Dilute
to mark with ASTM Type 1 water and mix again. After
40 minutes, read absorbance at 620 nm in a 1 cm
D-56 10/91
-------
Exhibit D Method 335.2
cell. NOTE: More than 0.5 mL of chloramine-T will
prevent the color from developing with pyridine-
pyrazolone.
6.1.2 Prepare a minimum of 3 standards and a blank by pipetting
suitable volumes of standard solution into 250 mL volumetric
flasks. MOTE: One calibration standard must be at the
Contract Required Detection Limit (CRDL). To each standard,
add 50 mL of 1.25 N sodium hydroxide and dilute to 250 mL with
ASTM Type I water. Standards must bracket the concentration of
the samples. If dilution is required, use the blank solution.
As an example, standard solutions could be prepared as follows:
mL of Standard Solution Cone, ug ON
(1.0 - 5 uy CN> per 250 mL
0 Blank
1.0 5
2.0 10
5.0 25
10.0 50
15.0 75
20.0 100
6.1.2.1 It is not imperative that all standards be distilled
in the same manner as the samples. At lease one
standard (mid-range) must be distilled and compared
to similar values on the curve to ensure that the
distillation technique is reliable. If the distilled
standard does not agree within ±15% of the
undistilled standards, the operator should find and
correct the cause of the apparent error before
proceeding.
6.1.2.2 Prepare a standard curve by plotting absorbance of
standard vs. cyanide concentrations (per 2SO mL).
6.2 Semi-Automated Spectrophotometric Determination (Option C)
6.2.1 Set up the manifold. Pump the reagents through the system
until a steady baseline is obtained.
6.2.2 Calibration standards: Prepare a blank and at least three
calibration standards over the range of the analysis. One
calibration standard must be at the CRDL. For a working range
of 0-200 ug/L, the following standards may be used:
D-57 10/91
-------
Exhibit D Method 33S.2
mL Standard Solution Concentration
diluted to 1 liter ug CN/L
0 0
4.0 20
10.0 SO
20.0 100
30.0 ISO
40.0 200
Add 10 g of NaOH to each standard. Store at 4*C(±2*C)
6.2.3 Place calibration standards, blanks, and control standards in
the sampler tray, followed by distilled samples, distilled
duplicates, distilled standards, distilled spikes, and
distilled blanks.
6.2.4 When a steady reagent baseline is obtained and before starting
the sampler, adjust the baseline using the appropriate knob on
the colorimeter. Aspirate a calibration standard and adjust the
STD GAL dial on the colorimeter until the desired signal is
obtained. Record the STD CAL value. Re-establish the baseline
and proceed to analyze calibration standards, blanks, control
standards, distilled samples, and distilled QC audits.
7. CALCTJLATIOHS
7.1 If the semi-automated method is used, measure the peak heights of the
calibration standards (visually or using a data system) and calculate a
linear regression equation. Apply the equation to the samples and QC
audits to determine the cyanide concentration in the distillates. To
determine the concentration of cyanide in the original sample, MULTIPLY
THE RESULTS BY ONE-HALF (since the original volume was 500 mL and the
distillate volume was 250 mL). Also, correct for any dilutions which
were Bade before or after distillation.
7.2 If the colorimetric procedure is used, calculate the cyanide, in ug/L,
in the original sample as follows:
A x 1,000 mL/L x
CN. ug/L -
Where: A - ug CN read from standard curve (per 250 mL
B - mL of original sample for.distillation
C - mL taken for colorimetric analysis
50 mL - volume of original sample aliquot
1,000 oL - conversion mL to L
7.3 Appropriate concentration units must be specified on the required
forms. The quantitative values shall be reported in units of
micrograms per liter (ug/L) for aqueous samples, NO other units are
acceptable. . '. . ''...•
D-58 10/91
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Exhibit D Method 335.2
7.4 If dilutions were performed, the appropriate corrections mast be
applied to the sample values.
8. QUALITY CONTROL
8.1 Quality control must be performed as specified in Exhibit E.
8.2 All quality control (QC) data must be submitted with each data package
as specified in Exhibit B.
9. BtfBRKffCZS
9.1 Interim Methods for the Sampling and Analysis of Priority Pollutants in
Sediments and Fish Tissue," USEPA Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio, August 1977, Revised October 1980.
9.2 Methods for "Chemical Analysis of Water and Wastes', March 1979. EPA
publication *600/4-79-02.
9.3 Op. cit. (#4), Methods 335.2.
9.4 "Operation RN Manual for Technicon Auto Analyzer IIC System*, 1980.
Technical publication #TA9-0460-00. Technicon Industrial Systems,
Tarrytown, NY, 10591.
9.5 "Users Guide for the Continuous Flow Analyzer Automation System", EMSL
U.S. EPA, Cincinnati, OH (1981).
D-59 10/91
-------
Exhibit 0 We nod 300.0
PART H
ION CHROKATOGRAPHY METHOD FOR H02/NO3-H
1. SCOPE ASP APPLICATION
1.1 This method is applicable to the detemination of N02/NOj-N in low
concentration water samples.
1.2 The range of the method nay be varied through instrument and/or sample
size. Using a 100 uL sample size, a detection limit of 10 ug/L for
N02/N03-N can be achieved.
1.3 This method is restricted to use by or under the supervision of
analysts experienced in the use of ion chromatography and in the
interpretation of the resulting ion chromatogram.
2. SUMMARY OF METHOD
2.1 A small volume of sample, typically 0.1 - 1.0 mL, is introduced into an
ion chroma tograph. The anions of interest are separated and measured
using a system comprised of a guard column, separator column,
suppressor column, and conductivity detector.
3.
3 . 1 Interferences can be caused by substances with retention times that are
similar to and overlap those of the anion of interest. Large amounts
of an anion can interfere with the peak resolution of an adjacent
anion. If it is determined that this type of interference cannot be
resolved, N02/N03-N must be determined by using the color ime trie method
specified in Part I.
3.Z Method interferences may be caused by contaminants in the reagent
water, reagents, glassware, and other sample processing apparatus that
lead to discrete artifacts or elevated baseline in ion chromatograms .
3.3 Samples that contain particles larger than 0.45 microns and reagent
solutions that contain particles larger than 0.20 microns require
filtration to prevent damage to instrument columns and flow systems.
3.4 The use of concentrated sulfuric acid, in the preservation of the
sample, can cause possible instrument interference problems in the
analysis of the target analyte. The analyst should be aware of the
type of preservative used and take the appropriate action, if
necessary. Sulfuric acid must be neutralized before proceeding with
the analysis.
4. APPARATUS
4.1 Ion chroma to graph: Any analytical system complete with ion
chromato graph and all required accessories including analytical
columns, detector, stripchart recorder and a data system for peak
integration.
D-60 10/91
-------
Exhibit D Method 300.0
4.1.1 Anion guard column: 4 x 50mm.
4.1.2 Anion separator column: 4 x 250nm.
4.1.3 Anion suppressor column: fiber, or equivalent.
4.1.4 Detector: Conductivity cell, approximately 6 ul volume.
4.2 Operational Requirements
4.2.1 Because of the differences between various makes and models of
satisfactory instruments, no detailed operating instructions
can be provided. Instead, the analyst should follow the
instructions provided by the manufacturer of die particular
instrument. Other columns, chromatographic conditions, or
detectors may be used if the QA requirements in Exhibit E are
met. Sensitivity, instrumental detection limits, precision,
retention time and other column chromatographic conditions must
be investigated and established for iK>2/NO3-N on that
particular instrument.
IT IS THE RESPONSIBILITY OF THE ANALYST TO VERIFY THAT THE
INSTRUMENT CONFIGURATION AND OPERATING CONDITIONS USED SATISFY
THE ANALYTICAL REQUIREMENTS SET FORTH IN THIS METHOD AND TO
MAINTAIN QUALITY CONTROL DATA CONFIRMING INSTRUMENT PERFORMANCE
AND ANALYTICAL RESULTS.
The data must include hardcopies or computer readable storage
media which can be readily examined by an audit team. The data
must demonstrate defendable choices of instrument operating
conditions which minimize interferences such as sulfide co-
elution.
5. BEAgBBTS AND STANDARJ?
5.1 Reagent water: ASTH Type I water, free of anions of interest and
containing no particles larger than 0.20 microns.
5.2 Eluent solution: Sodium bicarbonate 0.003 K, sodium carbonate 0.0024
M. Dissolve 1.0081 g sodium bicarbonate (NaHCO3) and 1.0176 g of
sodium carbonate (Na2CO;j) in reagent water and dilute to 4 liters.
5.2.1 Eluent spiking solution: sodium bicarbonate 0.030 M, sodium
carbonate 0.0240 M. Dissolve 2.5203 g sodium bicarbonate
(NaHCO3) and 2.5440 g of sodium carbonate (NA2CC>3) in reagent
water and dilute to 1 liter.
5.3 Regeneration solution (fiber suppressor, or equivalent): Sulfuric acid
0.025 N. Dilute 8 mL cone, sulfuric acid (H^SO/^) to 4 liters with
reagent water.
5.4 Stock standards, 1000 mg/L: Stock standard solutions may be purchased
as certified solutions or prepared from ACS reagent grade materials
(dried at 105*C for 30 minutes) as listed below.
D-61 10/91
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Exhibit 0 Method 300.0
5.4.1 N02/N03-N 1000 mg/L: dissolve 6.0679 g of sodium nitrate
(NaN03) and 4.9257 g sodium nitrite (NaNO2) in reagent water
and dilute to 1 liter.
6.1 Establish a stable baseline with working eluent running through the
system and establish ion chromatographic operating parameters
equivalent to obtain the CRDL's. This requires at least 30 minutes.
6.2 Calibration and Sample Analysis
6.2.1 Matrix matching, with the samples, is mandatory for all blanks,
standards, and quality to control samples to avoid inaccurate
concentration values due to possible standard curve deviation.
6.2.2 For N02/M03-N, prepare a combined calibration standard at a
minimum of three concentration levels and a blank by adding
accurately measured volumes of the stock standards to a
volumetric flask and diluting to volume with reagent water.
One of the standards must be at the CRDL. The attenuator range
settings must be linear.
6.2.3 Using injections of 0.1 to 1.0 mL (determined by injection loop
volume) of each calibration standard, tabulate peak height or
area responses against the concentration. The results are used
to prepare a calibration curve for each analyte. During this
procedure, retention times must be recorded.
6.2.4 The working calibration curve must be prepared daily and
whenever the anion eluent is changed and after every 20 samples
whichever is most frequent. If the response for any analyte
varies from the expected values by more than ±10%, the test
must be repeated, using fresh calibration standards. If the
results are still more than ±10%, an entire new calibration
must be prepared for that analyte. Nonlinear response can
result when the separator column capacity is exceeded
(overloading). Maximum loading (all anions) should not exceed
400 ppm.
6.2.5 The width of the retention time window used to make
identifications must be based upon measurements of actual
retention time variations of standards run over three non-
consecutive days. Three times the standard deviation will be
used to calculate the retention time windows. The retention
time for N02/N03-M must be within the retention time window
established during the most recent initial calibration. A.
retention time window of 1% of the average retention time of
the three standards must be used if the computed one is less
Chan 1% of that average.
D-62 10/91
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Exhibit 0 Method 300.0
6.2.6 Load and inject a fixed amount of sample, using the same size
loop for standards and samples. Flush the injection loop
thoroughly, using each new sample. Record the resulting peak
size in area or peak height units. An automated sampler system
may be used.
6.2.7 If the response for the peak exceeds the linear range of the
system, dilute the sample with an appropriate amount of reagent
water (but not below the CRDL) and reanalyze.
7. CALCULATIONS
7.1 Prepare separate calibration curves for N02/N03-N by plotting peak size
in area, or peak height units of standards against concentration.
Compute sample concentration by comparing sample peak response with the
standard curve.
7.2 If dilutions were performed, the appropriate factor must be applied to
sample values.
7.3 Appropriate concentration units must be specified on the required
forms. The quantitative values shall be reported in units of
micrograos per liter (ug/L) for aqueous samples. NO other units are
acceptable.
8. OTAIJT* COaTTML
8.1 Quality control must be performed as specified in Exhibit E.
8.2 All quality control (QC) data must be submitted with each data package
as specified in Exhibit B.
8.3 Reportable data for a sample must include a chromatogram with retention
times within the retention time windows established during the most
recent initial calibration. If identification of specific anions is
questionable, the samples must be reanalyzed by other methods listed
within this contract.
D-63 10/91
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Exhibit D Methou 253.2
PART I
AUTOMATED COLORIMETRIC METHODS FOR THE DETERMINATION OF B02/NO3-N
1. SCOPE AND APPLICATIfHf
1.1 This method is applicable to the determination of 1K>2/NO3-N in low
concentration water samples.
1.2 The range of this method is 50 to 10000 ug/L K02/N03-N.
2. STP«*m»T OF METHOD
2.1 A filtered sample is passed through a column containing granulated
copper-cadmium to reduce nitrate to nitrite. The nitrite (that
originally present plus reduced nitrate) is determined by diazotizing
with sulfanilamide and coupling with N-(l-naphthyl)-ethylenediamine
dihydrochloride to form a highly colored azo dye which is measured
colorimetrically.
3.
3.1 Build up of suspended matter in the reduction column will restrict
sample flow.
3.2 Low results might be obtained for samples that contain high
concentrations of iron, copper or other metals. EDTA is added to the
saaples to eliminate this interference.
3.3 Samples that contain large concentrations of oil and grease will coat
the surface of the cadmium. This interference can be eliminated by
pre-extracting the sample with an organic solvent.
4.
4.1 Auto analyzer system with the following components:
4.1.1 Sampler.
4.1.2 Proportioning pump.
4.1.3 Nitrate-nitrite analytical cartridge.
4.1.4 Chart recorder .
4.1.5 Colorimeter with 50 mm tubular flow cell and 540 mm filter.
4.2 Operational Requirements
4.2.1 System Configuration -- Because of the differences between
various makes and models of satisfactory instruments, no
detailed operating instructions can be provided. Instead, the
analyst should follow the instructions provided by the
manufacturer of that particular instrument. Sensitivity,
D-64 10/9i
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Exhibit 0 Method 353.2
instrumental detection limit, precision, linear dynamic range,
and interference effects must be investigated and established
for -itrate and nitrice on thar. particular instrument.
IT IS THE RESPONSIBILITY OF THE ANALYST TO VERIFY THAT THE
INSTRUMENT CONFIGURATION AND OPERATING CONDITIONS USED SATISFY
THE ANALYTICAL REQUIREMENTS SET FORTH M THIS METHOD AND TO
MAINTAIN QDALITT CONTROL DATA CONFIRMIIIC INSTRUMENT PERFORMANCE
ARD ANALYTICAL RESULTS.
5. MACElfTS AMD STANDARDS
S.I Granulated cadad.ua: 40-60 mesh.
5.2 Copper-cadaiua: The eadaiua granules (new or used) are cleaned with
dilute HC1 and copperized with 2% solution of copper sulfaCe in the
following aanner:
5.2.1 Wash the eadaiua with 6N HC1 and rinse with ASTM Type I water.
The color of the eadaiua so treated should be silver.
5.2.2 Swirl lOg eadaiua in 100 aL portions of 2% solution of copper
sulfate for five ainutes or until blue color partially fades,
decant, and repeat with fresh copper sulfate until a brown
colloidal precipitate foras.
5.2.3 Wash the cadaiua-copper with ASTM Type I water (at least ten
tines) to reaove all precipitated copper. The color of the
eadaiua so treated should be black.
5.3 Color reagent: To approximately 800 mL of ASTM Type I water, add, while
stirring, 100 aL cone, phosphoric acid, 40g sulfanilaaide, and 2g N-l-
naphthylethylenediaaine dihydrochloride. Stir until dissolved and
dilute to one liter. Store in brown bottle and keep in the dark when
not in use. This solution is stable for several months.
5.4 Dilute hydrochloric acid, 6N: Dilute 50 aL cone. HC1 to 100 aL with
ASTM Type I water.
5.5 Copper sulfate solution, 2%: Dissolve 20g of CuSO^-l^O in 500 aL of
ASTM Type I water and dilute to one liter.
5.6 Ammonium chloride-EDTA solution: Dissolve 85g of reagent grade ammonium
chloride and O.lg of disodium ethylenediaaine tetracetate in 900 mL of
ASTM Type I water. Adjust the pH to 8.5 with cone, amaoniua hydroxide
and dilute to one liter. Add 1/2 mL of a surfactant.
5.7 Stock standard solutions. 1000 mg/L (Img/mL): Stock standard solutions
may be purchased as certified solutions or prepared from ACS reagent
grade aaterials (dried at 105*C for 30 min.) as listed below.
5.7.1 Nitrate (N03-N) 1000 mg/L: Dissolve 6.0679g sodium nitrate
in ASTM Type I water and dilute to one liter.
D-65 10/91
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Exhibit D Method 353.2
6. PROCEDURE
6.1 Calibration and Sample Analysis
6.1.1 Matrix matching, with the saaples. is mandatory for all blanks,
standards, and quality control saaples to avoid inaccurate
concentration values due to possible standard curve deviations.
6.1.2 Set up the manifold. Pump the reagents through the system
until a steady baseline is obtained.
6.1.3 Prepare a blank and at least three standards over the suspected
range of analysis. One calibration standard oust be at the
CRDL.
6.1.4 Saaples oust be neutralized (if the pH is below 5, froa
sulfuric acid preservation, or above 9) prior to analysis using
either concentrated HC1 or NH^OH. The saaples, standards, all
QC samples, and dilution water oust be matrix matched.
6.1.5 Place calibration standards, blanks, and quality control
standards in the sampler tray, followed by samples.
6.1.6 When a steady baseline is obtained and before starting the
sampler, adjust the baseline, using the coloriaeter, to zero.
Aspirate a calibration standard and adjust the coloriaeter
until the desired maximum signal is obtained. Re-establish the
baseline and proceed to analyze the calibration standards,
blanks, quality control standards, and samples.
6.1.7 Prepare standard curve by plotting absorbance peak heights of
processed standards against known concentrations. The curve
must have a correlation coefficient greater than or equal to
0.99S. If the correlation coefficient is less than 0.995, the
analysis must be repeated.
6.1.8 Dilute and reanalyze samples that are more concentrated than
the linear range for an analyte.
7.
7.1 Compute concentration of samples by comparing sample peak heights with
standard curve.
7.2 If dilutions were performed, Che appropriate factor must be applied to
saaple values.
7.3 .Appropriate concentration units must be specified on the required
forms. The quantitative values shall be reported in units of
micrograms per liter (ug/L) for aqueous samples, NO other units are
acceptable.
D-66 10/91
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Exhibit D Method 353.2
COHTROL
8.1 Quality control oust be performed as specified in Exhibit E.
8.2 All quality control (QC) data must be, submits '.th each data package
as specified in Exhibit B.
D-67 10/91
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Exhibit D Method 340.2
PART J
ION SELECTIVE ELECTRODE METHOD FOR THE DETERMTHATIOH OF FLUORIDE
1. SCOPE AJD
1.1 This method is applicable to the measurement of fluoride in low
concentration water samples.
1.2 The range of the method is 0.1 to 1000 mg/L of fluoride.
1.3 This method may not measure total fluoride.
2. SUMMARY OF METHOD
2.1 The fluoride is determined potentiometrically using a fluoride
electrode in conjunction with a standard single junction sleeve -type
reference electrode and a potentiometric meter having an expanded
millivolt scale.
2.2 The fluoride electrode consists of a lanthanum fluoride crystal across
which a potential is developed by fluoride ions.
3. Aff rmr BMP* :Bt>
3.1 Extremes of pH interference; sample pH should be between S and 9.
Polyvalent cations of Silicon, Iron, and Aluminum interfere by forming
complexes with fluoride. The degree of interference depends upon the
concentration of the complexing cations, the concentration of fluoride
and the pH of the sample. The addition of a pH S.O buffer containing a
strong chelating agent preferentially complexes aluminum (the most
common interference), silicon and iron. and eliminates the pH problem.
4.
4.1 Selective ion meter
4.2 Fluoride Ion Activity Electrode
4.3 Reference electrode, single junction, sleeve type.
4.4 Magnetic stirrer, teflon coated stirring bar
4.5 Operational Requirements
4.5.1 System Configuration -- Because of the differences between
various makes and models of satisfactory instruments, no
detailed instructions can be provided. Instead, the analyst
should follow the instructions provided by the manufacturer of
the particular instrument. Sensitivity, instrumental detection
limit, precision, linear dynamic range, and interference
effects must be investigated and established for fluoride on
that particular instrument.
D-68 10/91
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Exhibit D Method 340.2
IT IS THE RESPONSIBILITY OF THE ANALYST TO VERIFY THAT THE
INSTRUMENT CONFIGURATION AND OPERATING CONDITIONS USED SATISFY
THE ANALYTICAL REQUIREMENTS SET FORTH IN THIS METHOD AND TO
MAINTAIN QUALITY CONTROL DATA CONFIRXING INSTRUMENT PERFORMANCE
AND ANALYTICAL RESULTS.
5 _ BEACEPTS AND STANDARDS
5.1 Buffer solution, pH 5.0 - 5.'5: To approximately 500 nL of distilled
water in a 1 liter beaker add 57 mL of glacial acetic acid, 58 g of
sodium chloride and 4g of CDTA (1,2-cyclohexylene dinitrilo tetraacetic
acid). Stir to dissolve and cool to room temperature. Adjust pH of
solution to between 5.0 and 5.5 with 5 N sodiu» hydroxide (ABOUT 150 ML
WILL BE REQUIRED). Transfer solution to a 1 liter volumetric flask and
dilute to nark with ASTM Type I water.
5.2 Fluoride (F*) stock solution, 100 mg/L: Dissolve .2210g of sodium
fluoride in ASTM Type I water and dilute to 1 liter.
5.3 Sodium hydroxide, 5 N: Dissolve 200g sodium hydroxide in ASTM Type I
water, cool and dilute to 1 liter.
6. PROCEDURE;
6.1 Calibration and Sample Analysis
6.1.1 Matrix matching, with the samples, is mandatory for all blanks,
standards, and quality control samples to avoid inaccurate
concentration values due to possible standard curve deviations.
6.1.2 Prepare at least four standards using the fluoride stock
solution. The standards must be at the following
concentrations: .1 mg/L, 1.0 mg/L, 2.0 mg/L, and at the CRDL.
A blank standard does not need to be part of the calibration
curve since the log of zero is undefined. However, a blank
standard must be run immediately after calibration and it must
yield a concentration value of less than 0.1 mg/L.
6.1.3 Place 50 mL of sample or standard solution and 50 mL of buffer
in a. 150 mL beaker. Place on a magnetic stirrer and mix at
medium speed. Immerse the electrodes in solution and observe
the meter reading while mixing. The electrodes must remain in
solution for at least three minutes. Once the meter has
stabilized, a reading may be obtained. At concentrations under
0.5 mg/L F, it may require five minutes or more to reach a
stable meter reading.
6.1.& Dilute and reanalyze samples that are more concentrated than
the linear range for an analyte.
D-69 10/91
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Exhibit 0 Method 340.2
7. CALCTIATIOHS
7.1 Using semi logarithmic graph paper, plot che concentration of fluoride
in ug/L on che log axis vs. che electrode potential developed in Che
standard on che linear axis, starting with the lowest concentration at
che bottom of the scale. If the instrument has the capability,
fluoride concentracion nay be read directly fro* the meter.
7.2 If dilutions were performed, the appropriate factor Bust be applied to
the sample value.
7.3 Appropriate concentration units must be specified on the required
forms. The quantitative values shall be reported in units of
micrograms per liter (ug/L) for aqueous samples, MO other units are
acceptable.
8.1 Quality control must be performed as specified in Exhibit E.
8.2 All quality control (QC) data must be submitted with each data package
as specified in Exhibit B.
D-70 10/91
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QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
10/91
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This section outlines the «inimum QA/QC operations necessary to satisfy the
analytical requirements of the contract. The following QA/QC operations oust
be performed as described in this Exhibit:
1. ICP/HS Tuning; and Mas* uiiibration
2. Retention Time Window for Ion Chronatography
3. Instrunent Calibration
4. Initial Calibration Verification (ICV) and Continuing Calibration
Verification (CCV)
5. CRDL Standards (CRI)
6. Linear Range Standard Analysis (LRS)
7. Initial Calibration Blank (ICB), Continuing Calibration Blank (CCB),
and Preparation Blank (PB) Analyses
8. ICP and ICP/MS Interference Check Saaple (ICS) Analyses
9. Matrix Spike Saaple Analysis (S)
10. Duplicate Sample Analysis (D)
11. Laboratory Control Saaple (LCS) Analysis
12. Performance Evaluation Saaple (PES)
13. Serial Dilution Analysis (L)
14. Internal Standards for ICP/MS
IS. Instrument Detection Limit (IDL) Determination
16. Intereleaent Corrections for ICP and ICP/MS
17. Hydride ICP (HYICP) and Furnace AA QC Analysis
1. ICP/MS TUBUHG AHD MASS CALIBRATION
1.1 Guidelines for mass calibration and tuning are given in Exhibit D.
Resolution and mass calibration oust be performed for each ICP/MS
system, each time the instrument is set up. The resolution and Bass
calibration oust be verified immediately before instrument calibration.
The resolution and mass calibration must also be verified at the end of
each analytical run, or every eight hours, which ever is more frequent.
The tuning solution must be analyzed after the final CCV/CCB in the
run. The mass calibration and tuning times as well as their
verification tines must be included in the raw data.
A 100 ppb solution of elements Li, Co, In, and Tl must be used as a
tuning verification solution. The intensities and isotopic ratios of
the tuning criteria are as recommended in Table VIII, Exhibit C. The
resolution and mass calibration criteria must be within the control
limits in Table VIII, Exhibit C. If not, the analysis must be
terminated, the problem corrected and all measurements taken by the
instrument since the last compliant mass calibration and resolution
check must be reperformed in a new analytical run.
E-l 10/91
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1.2 The values for Che initial and subsequent mass calibrations and
resolution cheek shall be recorded on Fora XIV - LCIN for ICF/MS
analyses, as indicated in Exhibit B.
2. RETENTION TIME glHPQg FOR ION CHROMATOCRAPH^
2.1 Retention tine windows for all analytes analyzed using Ion
Chroma tography (1C) must be established prior to any sample analysis
and each tine a new column is installed. The width of the retention
tine window used to establish identification Bust be based upon
measurement of actual retention times of standards run over three non-
consecutive days. The concentration of each standard oust be
sufficient to produce a response for each analyte that is approximately
half scale. Three times the standard deviation of the retention time
of the standards shall be used to calculate the retention time windows
for each analyte. A retention time window of 1% of the average
retention time of the three standards must be used if the computed one
is less than 1% of that average.
The retention time window must be individually determined for each
analysis run by measuring the retention time of the calibration
standard near the aid range of the calibration curve for that run and
making that retention time the center of the established retention time
window (see Exhibit B) . The retention time of each measured value for
each analyte must be within the retention time window established
during the most recent instrument calibration for that analyte. If
not, the analysis must be stopped, the problem corrected, the
instrument recalibrated, new retention time windows determined, and the
samples analyzed since the last compliant CCV must be reanalyzed in a
new run.
Retention times must be calculated and reported for each measurement
taken for each analyte analyzed by 1C.
2.2 The values for the retention time and retention time windows must be
reported on Form XVII - LCIN for all analytes analyzed by 1C systems ,
as indicated in Exhibit B.
3. IMSTMMaiT CALIBRATION
3.1 Guidelines for instrumental calibration are given in EPA 600/4-79-0201
and/or Exhibit 0. Instruments must be calibrated daily or once every
24 hours (8 hours for ICP/MS) and each time the instrument is set up.
The instrument standardization date and time must be reported in the
raw data.
Calibration standards must be prepared by diluting the stock solutions
at the time of analysis, and be discarded after use. The date and time
of preparation and analysis of the standards must be reported in the
raw data.
The calibration standards must be prepared using the same type of
matrix and at the same concentration as in the preparation blank
following preparation. Aspirate, inject, or immerse the electrodes in
E-2 10/91
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the calibration solutions as described in the individual Methods (see
Exhibit D) , and record the readings for each analyte at each
wavelength, mass, detector configuration, and potential used for
analysis in the SDG.
Calibrate all systems according to the instrument manufacturer's
recommended procedures or as specified in Exhibit D. At least one
blank and a standard must be used for ICP, HYICP, and ICP/MS systems.
All other systems must have a calibration standard at the CRDL, a
blank, and at least two other standards. Systems that use non- linear
calibration curves must use at least three additional standards which
cover both the upper and lower ranges of the curve.
All calibration curves must have a correlation coefficient of 0.9950 or
greater before any analysis may be started. The correlation
coefficient for each calibration curve must be clearly documented and
must be submitted with the raw data.
3 . 2 Baseline correction is acceptable as long as it is performed after each
and every sample, or after the continuing calibration verification and
blank check.
4 IHITIAL CALIBRATTOfl V^mCATIOH (ICV^ AND COBTIHUIHC CAUBRATIOH
(CCV)
4.1 Initial Calibration Verification (ICV)
4.1.1 Immediately after each of the analysis systems have been
calibrated, the accuracy of the initial calibration must be
verified and documented for each and every analyte by the
analysis of Initial Calibration Verification Solution(s) . When
resulting measurements exceed the control limits of Table III-
Initial and Continuing Calibration Verification and CRDL
Standard Control Limits for Inorganic Analyses (see Exhibit C),
the analysis must be terminated, the problem corrected, the
instrument recalibrated, and the calibration reverified.
4.1.2 If the Initial Calibration Verification Solution(s) are not
provided, or where a certified solution of an analyte is not
available from any source, analyses must be conducted on an
independent standard at a concentration other than that used
for regular instrument calibration, but within the calibration
range. An independent standard is defined as a standard
composed of the analytes from a. different source than those
used in the standards for the instrument calibration.
4.1.3 For ICP, HYICP. ICP/MS and AA the Initial Calibration
Verification Solution(s) oust be run and reported at each
wavelength and elemental expression used for analysis. For
cyanide, the initial calibration verification standard must be
distilled. The Initial Calibration Verification for cyanide
serves as a Laboratory Control Sample; thus it must be
distilled .with the batch of samples analyzed in association
* . •. . •
E-3 10/91
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with that ICV. This means that an ICV must be distilled with
each batch of samples analyzed and that the samples distilled
with an ICV must be analyzed with that particular ICV.
4.2 Continuing Calibration Verification (CCV)
4.2.1 To ensure calibration accuracy during each analysis run, one of
the following standards is to be used for continuing
calibration verification and must be analyzed and reported for
each analyte, at a frequency of 10% or every 2 hours during an
analysis run, whichever is more frequent. The standard
solution must also be analyzed at the beginning of the run and
after the last analytical sample.
4.2.2 If more than one wavelength or elemental expression is used to
produce results for an analyte, the continuing calibration
verification must be analyzed and reported for every wavelength
and elemental expression used to produce results for that
analyte in the SDG.
4.2.3 The analyte concentrations in the continuing calibration
standard must be one of the following solutions at or near
(±10%) the mid-range levels of the calibration curve:
1. Provided solutions
2. A Contractor ^prepared standard solution
The same continuing calibration standard must be used
throughout the analysis runs for an SDG received.
4.2.4 Each CCV analyzed most reflect the conditions of analysis of
all associated analytical samples (the preceding 10 analytical
samples or the preceding analytical samples to the previous
CCV). The duration of analysis. rinses and other related
operations that may affect the CCV measured result may not be
applied to the CCV to a greater extent than the extent applied
to the associated analytical samples. For instance, the
difference in time between a CCV analysis and the blank
immediately following it, as well as the difference in time
between the CCV and the analytical sample immediately preceding
it. may not exceed the smallest difference in time between any
two consecutive analytical samples associated with the CCV.
4.2.S If the deviation of the continuing calibration verification is
greater than the control limits specified in Table 111 in
Exhibit C. the analysis must be terminated, the problem
corrected and the CCV reanalyzed only once. If the first
reanalysis yields a CCV value within control limits, then the
preceding 10 analytical samples or all analytical samples
analyzed since the last compliant calibration verification may
be reanalyzed for the analytes affected. Otherwise the
instrument must be recalibrated, the calibration verified and
the affected analytical samples rerun in the context of a new
run. If the affected analytical sample is an instrument
E-4 10/91
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related QC sample such as ICS, CRI, or LRS, then the correction
to the problem and reanalysis of the standards must be done
immediately within the 8 hour limit for those standards. If
not, reanalysis of all samples and QC samples in the run is
required.
4.2.6 Each analytical sample must be preceded by a CCV. As many as
ten (10) analytical samples may be analyzed before a subsequent
CCV is required. However, the CCV must be reanalyzed within
two (2) hours. The values for each analyte in the two CCVs
must be within the control limits.
4.3 The values for the initial and subsequent continuing calibration
verification must be recorded on Form II - LCIN for all analysis
systems, as indicated in Exhibit B.
5. 9RJL STAHDABP (CRI)
5.1 To verify linearity near the IDL for all analysis systems, the
Contractor must analyze a standard at two times the CROL at the
beginning and end of each sample analysis run, or a minimum of twice
per 8 consecutive hours, whichever is more frequent, but not before
Initial Calibration Verification. The CRI standard must be run for
each analyte at every wavelength and elemental expression used for
analysis .
5.2 All results for the analysis of the CRDL standard must fall within the
control limits specified in Table III in Exhibit C for each analyte at
every wavelength and elemental expression used for analysis. If not,
the analysis must be terminated, the problem corrected and all
analytical samples since the last compliant CRI reanalyzed.
5.3 The values for Che initial and subsequent CRDL standards must be
recorded on Font III • LCIN for all analysis systems, as indicated in
Exhibit B.
6. LIHEAR. *Ajyyy AHALTSIS STAHPABJ ftf ?)
6.1 To verify the upper limit of the linear range of all analysis systems,
the Contractor must analyze a standard at the upper limit of the linear
range of ICF. HYICP. and ICP/MS systems and at the concentration of the
highest calibration standard for all other analysis systems. The
linear range standard must be analyzed at the beginning and end of each
sample analysis run, or a minimum of rwice per 8 consecutive hours,
whichever is more frequent, but not before Initial Calibration
Verification. This standard must be run for each analyte at every
wavelength or elemental expression used for analysis.
6.2 Results for the analysis of the .LRS must fall within the control limits
of ±10% of the true value for each analyte at every wavelength and
elemental expression used for analysis. If not, the analysis must be
terminated and successive dilutions of the standard must be reanalyzed
until the control limits are met. The concentration of this standard
E-5 10/91
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that meets the control limits is the upper limit of the instrument
linear range beyond which results cannot be reported under this
contract without dilution of the analytical sample.
6.3 values for the initial and subsequent linear range standards must
be recorded on Form IV - LCIN for all analysis systems, as indicated in
Exhibit B.
7. INITIAL CALIBRATION VERIFICATION BLANK (ICB) . COHTIHDIBC 7ALIBRATION
I ITJUnt fCCll^ AMD mmARATTOM MTJUir fVBA AHAT.TCITC
Three types of blanks are used for analysis. The calibration blank is
used in establishing and checking the calibration curve, the
preparation blank is used to monitor for possible contamination
resulting from the sample preparation procedure, and the rinse blank
(if appropriate) is used to flush the system between all samples and
standards.
7.1 Initial Calibration Verification Blank (ICB) and Continuing Calibration
Verification Blank (CCB) Analyses
7.1.1 A calibration blank must be analyzed for each analyte at each
wavelength and elemental expression used for analysis,
immediately after each and every initial and continuing
calibration verification, linear range standard and memory test
solution (MTS). see Exhibit D (Part E) and Exhibit C (Table
IX), at a frequency of 10% or every 2 hours during the run,
whichever is more frequent. The blank must be analyzed at the
beginning of the run and after the last analytical sample.
Note: A CCB must be run after the last CCV that was run after
the last analytical sample of the run.
7.1.2 If more than one wavelength or elemental expression instrument
setting is used to produce results for an analyte, the Initial
and Continuing Calibration blanks must be analyzed and reported
for every wavelength and elemental expression used to produce
results for that analyte in the SDG.
7.1.3 If the magnitude (absolute value) of the calibration blank
result exceeds the IDL, the result must be so reported on Form
V - LCIN. If the absolute value of the blank result exceeds
the CRDL. analysis must be terminated, the problem corrected,
the instrument recalibrated and the preceding 10 analytical
samples or all analytical samples analyzed since the last
compliant calibration blank must be reanalyzed. The instrument
oust be recalibrated, the calibration verified and the affected
analytical samples rerun in the context of a new run. If any
of the affected analytical samples are instrument related QC
samples, such as ICS, CRI, LRS, or MIS, then the correction to
the problem and reanalysis of the standards must be done
immediately within the 8 hour limit for those standards. If
not, reanalysis of all samples and QC in the run is required.
E-6 10/91
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7.1.4 Each analytical sample must be preceded by a calibration blank.
As many as ten (10) analytical samples may be analyzed before a
subsequent CCB is required. However, the CCB must be
reanalyzed within two (2) hours. The absolute value for each
analyte in these two CCBs oust fall below the CRDL.
For ICP/MS systems, the flush time between any of the samples
in a run cannot be less than the flush time between the KTS and
the CCB that immediately follows it in the memory test for that
run. For all other analysis systems, the flush time between
any of the samples in a run cannot be less than the flush time
between the LRS and the CCB that immediately follows it in that
run.
For all analysis systems, flush time between any of the samples
in a QC set cannot be less than the flush time between the last
sample and the final CCB of that same set. A QC set is the set
of analytical samples analyzed between two consecutive CCV/CCB
sets.
Dry burns for Graphite Furnace AA are included in the flush
time. Rinses and other similar activities are also included in
the flush time for the purpose of this rule.
7.2 Preparation Blank (PB) Analysis
7.2.1 At least one preparation blank (or reagent blank), consisting
of ASTM Type I water processed through each sample preparation
and analysis procedure (See Exhibit D, Section III), must be
prepared and analyzed with every Sample Delivery Group, or with
each batch of samples prepared, whichever is more frequent.
7.2.2 If more than one preparation blank for the same method was
required, then the first batch of samples is to be associated
with preparation blank one, the second batch of samples with
preparation blank two, etc. Each data package must contain the
results of all the preparation blank analyses associated with
the samples in that SDG.
The preparation blanks are to be reported for each SDG and used
in all analyses to ascertain whether sample concentrations
reflect contamination in the following manner:
1) If the absolute value of the concentration of the
preparation blank is less than or equal to the CRDL
(Exhibit C) , no correction of sample results is performed.
2) If any analyte concentration in the blank is above the
CRDL, the lowest concentration of that analyte in the
A group of samples prepared at the same time.
E-7 10/91
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associated samples oust be lOx che blank conc«n*jc«tion.
Otherwise, all saaples associated with che blank with che
analyte 's concentration less than lOx the blank
concentration and above the CRDL, oust be redigestec* — 1
reanalyzed for that analyte. The sample coticentratiuu- *a
not co be corrected for che blank value.
3) If an analyte concentration in Che blank is below che
negative CRDL, Chen all samples associated with Che blank
with analyte concentration less Chan lOx CRDL must be
redigesced and reanalyzed.
7.2.3 The values for che inicial and concinuing calibration blanks as
well as Che preparation blank must be recorded on Font V - LCIN
for all analysis systems, as indicaCed in Exhibit B.
8. IQP AHP ICP/MS iinptyp^j[pcE CHEC ?) AHALTSIS
8.1 To verify incerelemenc and background correction factors, Che
Contractor must analyze and report Che results for the ICP Interference
Check Sample at che beginning and end of each, analysis run or a minimum
of twice per 8 consecutive hours, whichever is more f requeue, but not
before Inicial Calibration Verification. The ICP Interference Check
Sample must be obtained from EMSL/LV if available and be analyzed
according to che instructions supplied with the ICS.
The Interference Check Sample consist of two solutions: Solution A and
Solution AB. Solution A consists of the interf erents , and Solution AB
contains both che analytes and che interf erents . An ICS analysis
consists of analyzing both solutions consecutively (starting with
Solution A) for all wavelengths and elemental expressions used for each
analyce reported by ICP and ICP/MS.
The magnitude (absolute value) of the result of each non- interfering
analyce for che analyses of Solution A for ICP and ICP/MS systems may
not exceed the CRDL.
Results for the analyses of Solution AB during Che analytical runs mist
be within che control limit of ±20% of the true value for Che analytes
included in che Interference Check Samples. If not, terminate the
analysis, correct che problem, recalibrate the instrument, and
reanalyze the analytical samples analyzed since the last compliant: ICS.
If the ICP Interference Check Sample is not provided, independent ICS
must be prepared with interferent and analyte concentrations at the
levels specified in Table V- Initial and Continuing Calibration
Verification and CRDL Standard Control Limits For Inorganic Analyses
(see Exhibit C) .
If the concentrations of the interfering analytes in Solution A or AB
are above the linear range of the instrument, diluting Chose solutions
is permitted as long as the dilution does not cause the true value of
the interfering analytes to be less than 10% of the established linear
range .
E-8 10/91
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8.2 The values for che 1C? and ICP/MS interference check saaple must be
recorded on Forn VI - LCIN for all analysis systems, as indicated in
Exhibit B.
9. MATRIX SPIKE SAMPLE ANALYSIS (S)
9.1 The matrix spike sample analysis is intended Co provide information
about Che effect of Che sample matrix on Che preparation and
measurement methodology. The spike is added before Che sample
preparation (i.e., prior Co digestion or distillation). One spike
sample analysis per mechod muse be performed on each group of samples
for each Sample Delivery Group.
If Che spike analysis is performed on the same sample Chat is chosen
for che duplicate sample analysis, spike calculations must be performed
using che results of che sample designated as Che "original sample"
(see Section 10. Duplicate Sample Analysis). The average of Che
duplicate results cannot be used for the purpose of determining percent
recovery. Samples identified as field blanks must not be used for
spiked sample analysis. SMO may require that a specific sample be used
for Che spike sample analysis. This requirement is indicated on che
traffic reporc or other documents that are shipped Co che Contractor
with che samples, and muse be followed.
For Spike Sample Analysis each analyte must be spiked with a
concentration level in the Spiked Sample solution as indicated in Table
IV in Exhibit C.
If two analytical methods are used to obtain the reported values for a
given analyte within a Sample Delivery Group, Chen spike samples must
be run by each method used.
If che spike recovery is not within che limits of 75-125%, Che data of
all samples received associated with that spike sample and determined
by che same analytical mechod must be flagged with the leCCer "N" on
Form I- LCIN and VII - LCIN. An exception to Chis rule muse be
followed when che sample concentration exceeds Che spike concentration
by a factor of four or more. In such an event, che data must be
reported unflagged even if the percent recovery does not meet che 75-
125% recovery criteria.
In Che instance when there is more than one spike sample per mechod per
SDG. if one spike sample recovery is not within the control limits, all
samples of the same method in the SDG must be flagged.
Individual component percent recoveries (%R) are calculated as follows:
%Recovery - (SSR-SRI x 100
SA
Where, SSR - Spiked Sample Result
SR - Sample Result
SA - Spike Added
E-9 10/91
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when sample concentration is less Chan the instrument detection limit.
use SR - 0 only for purposes of calculating % Recovery. The spike
saaple results, sample results and t Recovery (positive, negative or
zero) must be reported on Form VII - LCIN for all analysis systems, as
indicated.
9.2 The values for the sample, spiked sample and the spike added shall be
recorded on Fora VII - LCIN for all analysis systems, as indicated in
Exhibit B
10. Pny|je^TE SAMPLE ANALYSIS (D>
10.1 One duplicate sample per method must be analyzed for each Sample
Delivery Group. Duplicates cannot be averaged for reporting on Form I
- LCIN.
Sample* identified as field blanks must not be used for duplicate
sample analysis. SMO may require that a specific sample be used for
duplicate sample analysis. This requirement is usually indicated on
the traffic report and must be followed. If two analytical methods are
used to obtain the reported values for the same element for a Sample
Delivery Group, duplicate samples must be run by each method used.
The relative percent differences (RFD) for each analyte are calculated
as follows:
RPD - IS - PI x 100
(S+D)/2
Where, RFD - Relative Percent Difference
S - First Sample Value (original)
D - Second Sample Value (duplicate)
A control limit of 20% for RPD must be used for original and duplicate
sample values greater than or equal to Sx IDL. A control limit of (+)
the IDL must be used if either sample or duplicate values is less than
Sx IDL, and the absolute value of the control limit (IDL) must be
entered in the "Control Limit" column on Form VIII - LCIN.
If one result is above the Sx IDL level and the other is below, use the
+ IDL criteria. If both sample values are less than the IDL, the RFD
is not reported on FORM VIII - LCIN.
If the duplicate sample results are outside the control limits, flag
all the data for samples received associated with that duplicate sample
with an "*" on Forms I - LCIN and IX - LCIN. In the instance where
there is more than one duplicate sample per SDG, if one duplicate
result is not within contract criteria, flag all samples of the st
method in the SDG.
10.2 The values for the sample and duplicate must be recorded on Fora VIII -
LCIN for all analysis systems, as indicated in Exhibit B.
E-10 10/91
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11. LABORATORY CONTROL SAMPLJ! CLCS) ANALYSIS
11.1 The Laboratory Control Sample (LCS) must be analyzed for each analyte
using the same sample preparation, analytical methods and QA/QC
procedures employed for the field samples received.
The LCS vill be provided for a period of at least nine months after
contract award. The LCS oust be prepared and analyzed ualng each of
the procedures applied to the analysis of field samples. If the LCS is
unavailable, other quality assurance check saatples or certified
materials traceable to HIST certified standards nay be used. The true
value for each analyte concentration in the LCS must not exceed the
instrument's linear range and must not be added at a concentration
lower than the contract required detection limit (CBOL) for that
analyte. One LCS must be prepared and analyzed for each group of
samples in a Sample Delivery Group, or for each batch of samples
prepared by the same method, whichever is more frequent.
If the results of the LCS are outside the control limits established by
SMO, the analysis must be terminated, the problem corrected, and the
samples associated with that LCS reprepared and reanalyzed. A control
limit of ±20% of the true value must be used if no control Halts are
provided with the LCS solution.
11.2 The values for the LCS must be recorded on Fora IX - LCIH for all
analysis systems, as indicated in. Exhibit B, Section II.
12. pg»*OMIAHCE gVALPATIOlf "fftMfUP (PES)
12.1 The Performance Evaluation Sample will assist SMO in monitoring
contractor performance. The PES may be designated as a single blind QC
material or as full volume samples along with other environmental
samples as a double blind. The laboratory will not be informed of the
analytes in the PES or their concentration and the PES will be analyzed
concurrently with all samples in the Sample Delivery Group.
The Contractor must dilute the PES to volume according to the
instructions that accompany the ampules to the laboratory.
The laboratory must prepare the samples for analysis using the sample
preparation procedures outlined in Exhibit D, Section III, Sample
Preparation. The PES will be analyzed as a TOTAL CONSTITUENT AHALYSIS.
Analysis of the PES will be in accordance with Exhibit D, Section IV,
Sample Analysis. All contract QC muse also be met.
In addition to PES dilution, preparation and analysis, the Contractor
will be responsible for correctly identifying and quantifying the
analytes included in the PES. SMO will notify the Contractor of
unacceptable performance. MOTE: Unacceptable performance for
identification and quantification of analytes in the PES is defined as
a score of less than 75 percent.
E-ll 10/91
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12.2 The analysis results for the FES oust be recorded on Form I • LCIN for
all analytes. Exhibit B, Section II explains the instructions for
completing the forms.
13. SERIAL DILUTION ANALYSIS (L)
13.1 In order to check for the presence of matrix interference, the
Contractor must analyze and report the results of the Serial Dilution
analysis. Except for HYICP, ICP/MS. and Furnace AA methods, one Serial
Dilution analysis per method must be performed for each Sample Delivery
Group. Identified field blanks mav not b.7 mtd for Serial Dilution
analvaia.
The Serial Dilution analysis is performed by diluting a prepared sample
aliquot five-fold (Sx or 1+4). The dilution must be performed on an
analyte by analyte bases. The serial dilution is the dilution of the
sample, or an aliquot of the sample, that contains a concentration
level of the analyte within the linear range.
If the analyte concentration in the field sample is sufficiently high
(minimally a factor of SO above the IDL), the Serial Dilution must
agree within 10% of the initial sample concentration determination
after correction for the five fold dilution. If the Serial Dilution
analysis for one or more analyte is not within 10%, a chemical or
physical interference effect must be suspected and the data for all
analytes exceeding the limit in the samples associated with that serial
dilution must be flagged with an "E" on Form X - LCIN and Form I -
LCIN.
13.2 The values for the Initial sample and serial dilution must be recorded
on Form X - LCIN for all analysis systems, as indicated in Exhibit B.
14.1 In order to check for the presence of physical interferences and
correct for them, the contractor must use, measure, and report the
results of the internal standards for each ICP/MS analysis performed.
A minimum of three internal standards, listed in Table X Exhibit C,
bracketing the mass range must be used. The intensity level of an
internal standard for each sample, duplicate, spike analysis and PES
must be greater than 30% and less than 125% of the intensity level of
the internal standard of the blank calibration standard solution (SO) .
If not, the sample mist be reanalyzed after performing a five fold
(1+4) dilution. If the percent relative intensity, %R, (see Exhibit B,
Part Q) remains less than 30% or greater than 125%, a physical
interference must be suspected, and the data on Form XV must be flagged
with an "E". The analytes affected by the interference must be flagged
with an "E" on Form I - LCIN. The analytes affected by the
interference must be listed in the comment section on the appropriate
Forms VII - LCIN and VIII - LCIN if the affected sample is a matrix
spike or duplicate.
E-12 10/91
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The intensity levels of the intern>- standards for the CCV and CCB
solutions must agree within ±20% of the intensity level of the internal
standard of the initial calibration blank standard solution (SO) . If
not, the analysis must be terminated, the problem corrected and the
CCV/CCB reanalyzed only once. If the ' reanalysis of a CCV/CCB
yields a %R value within control limits, Chen the analysis must be
stopped, the problem corrected, and the preceding 10 analytical samples
or all analytical samples analyzed since the last compliant calibration
verification may be reanalyzed for the analytes affected. Otherwise,
the instrument must be recalibrated, the calibration verified and the
affected analytical samples rerun in the context of a new run.
The intensity levels of the internal standards for the ICV and ICB
solutions must agree within ±20% of the intensity level of the internal
standard of the blank calibration standard solution (SO). If not, the
analysis must be terminated, the problem corrected, and a new
analytical run must be started.
14.2 The values for the Internal Standard Percent Relative Intensity (%R)
must be reported for each ICP/MS analysis on Form XV • LCIN as
indicated in Exhibit B.
15.
15.1 Before any field samples are analyzed under this contract, the
instrument detection limits (in ug/L) must have been determined for
each instrument used, no earlier than 30 calender days before the start
of contract analyses and at least quarterly (every 3 calendar months
thereafter) , and must meet the levels specified in Table I in Exhibit
C.
If a Contractor fails to adhere to the requirements listed in this
section, a Contractor may expect, but SHO is not limited to the
following actions: reduction of numbers of samples sent under this
contract, suspension of sample shipment to the Contractor, ICP/MS tape
audit, data package audit, an on-site laboratory evaluation, remedial
performance evaluation sample, and/or contract sanctions.
The Instrument Detection Limits (in ug/L) must be determined by
multiplying by three the average of the standard deviations obtained on
three nonconsecutive days (each analyte in reagent water) at a
concentration 3 times or 5 times the IDL, with seven consecutive
measurements. Each measurement oust be performed as though it were a.
separate analytical sample (i.e., each measurement must be followed by
a rinse and/or any other procedure normally performed between the
analysis of separate samples) . IDLs must be determined and reported
for each set of instrument parameters used in the analysis of samples,
including wavelengths in ICP, and elemental expressions in ICP/MS.
The quarterly determined IDL for an instrument must be used as the IDL
for that instrument during that quarter. If the instrument is adjusted
in any way that may affect the IDL, the IDL for that instrument must be
redete rained and the results submitted for use as the established IDL
for that instrument for the remainder of the quarter.
E-13 10/91
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IDLs must be reported for each instrument used on Form XII - LCIN and
submitted with each data package. If multiple instruments are used for
the analysis of an analyte within a Sample Delivery Group, the highest
IDL for the analyte must be used for reporting concentration values for
that Sample Delivery Group.
The Instrument Detection Limit for each analyte must be less than or
equal to the Contract Required Detection limit. An exception is
granted if the analyte concentration in the samples analyzed by an
instrument is greater than or equal to five times the reported
detection limit for that instrument.
IS.2 Instrument Detection Limits must be determined quarterly. The results
of that determination must be reported on Form XII - LCIN, and
submitted with each data package, for each and every instrument used to
produce data in the SDG. as indicated in Exhibit B.
16. Tim'iRfiTJT'FT ^BBETTTi01*5 TOR Icp *^P ICT/MS
16.1 The ICF and ICP/MS interelement correction factors must have been
determined within three months prior to beginning sample analyses under
this contract, and at least annually thereafter. Correction factors
for spectral and isobaric interferences must be determined at all
wavelengths and elemental expressions used for each analyte reported by
ICP and ICP/MS.
The correction factors must be determined under the same instrument
conditions used for sample analysis. If the instrument was adjusted in
any way that may affect the interelement correction factors, the
factors must be redetermined and the results submitted for use.
16.2 Interelement correction factors must be determined annually. The
results of that determination must be reported on Form XIII - LCIN, and
submitted with each data package, for all ICP and ICP/MS parameters,
for each and every instrument used to generate data in the SDG, as
indicated in Exhibit B.
17.
Because of the nature of the HYICP and Furnace AA techniques, the
procedures summarized in Figure 1 are required for quantitation.
(These procedures do not replace those in Exhibit D, but supplement the
guidance provided therein).
a. All results of HYICP and Furnace AA analyses must be within the
linear and calibration range respectively. In addition, all results
of analyses, except during full Methods of Standard Additions (MSA),
require duplicate exposures (injections for Furnace AA). Average
concentration values must be used on the Reporting Forms. A maximum
of 10 full sample analyses to a maximum 20 exposures or injections
nay be performed between each consecutive calibration verification
and blank. The raw data package must contain intensity (absorbance
for Furnace AA) and concentration value for both exposures
(injections for Furnace AA). the average value and the relative
E-14 10/91
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standard deviation (RSD) or coefficient of variation (CV) for each
analysis. For concentrations greater than IDL, the duplicate
exposure (injections for Furnace AA) readings must agree within 15%
RSD or CV, »."- the analytical sample must be rerun once (i.e., two
additional exposures or injections). If the readings are still out
of the 15% limit, flag the value reported of Form I - LCIH with an
•M". The "M" flag is required for the analytical spike as well as
the sample. If the analytical spike for * sample requires an "M"
flag, the flag must be reported on Form 1 - LCIM for that sample.
b. All HYICP and Furnace AA analyses for each analytical sample,
including those requiring an "H" flag, will require at least an
analytical spike to determine if the MSA will be required for
quantitation. The analytical spike2 will be required to be at a
concentration (in the sample) of 30% of the linear range of each
analyte. This requirement for an analytical spike will include the
LCS and the preparation blank. The LCS must be quantified from the
calibration curve and corrective action(i.e. redigestion), if
needed, taken accordingly. MSA is not to be performed on the LCS or
preparation blank, regardless of spike recovery results.) If the
preparation blank analytical spike recovery is out of control (85-
115%) , the spiking solution must be verified by respiking and
rerunning the preparation blank once. If the preparation blank
analytical spike recovery is still out of control limits, the
problem must be corrected and respiking and reanalysis of all
analytical samples associated with that blank must be performed. An
analytical spike is not required on the pre-digestion spike sample.
The analytical spike of a sample must be run immediately after that
sample. The percent recovery (%R) of the spike, calculated by the
same formula as Spike Sample Analyses (see Section 9), determines
how the sample will be quantified, as follows:
1) If the spike recovery is less than 40%, the sample must be
diluted by a factor of 5 and rerun with another spike. This
step must only be performed once. If, after the dilution, the
spike recovery is still <40%, report data from the initial
undiluted analysis and flag with an "E" to indicate
interference problems.
2) If the spike and the spike recovery is at or between 85% and
115%. the sample must be quantified directly from the
calibration curve and reported down to the IDL.
2
Analytical spikes are post-digestion spikes to be prepared prior to analysis
by adding a known quantity of the analyte to an aliquot of the prepared
sample. The unspiked sample aliquot must be compensated for any volume
change in the spike samples by addition of ASTM Type II water to the unspiked
sample aliquot. The volume of the spiking solution added must not exceed 10%
of the analytical sample volume.- This requirement also applies to MSA
spikes.
E-15 10/91
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. X
3) If the spike recovery is greater than 40% and less than 85%, or
greater than 115%, Che sample must be quantified by MSA.
c. The following procedures muse be incorporated into MSA analyses.
1) Data from MSA calculations must be within the linear range as
determined by the calibration curve generated at the beginning
of the analytical run.
2) The sample and three spikes must be analyzed consecutively for
MSA quantitation (the "initial* spike run data are specifically
excluded from use in the MSA quantitation). Only single
exposures (injections for Furnace AA) are required for MSA
quantitation.
Each full MSA counts as two analytical samples toward
determining 10% QC frequency (i.e.,. five full MSA* can be
performed between calibration verifications).
3) For analytical runs containing only MSAs, single exposures
(injections for Furnace AA) can be used for QC samples during
that run. For instruments that operate in an MSA mode only,
MSA can be used to determine QC samples during that run. This
option must be used consistently.
4) Spikes must be prepared such that:
a) Spike 1 is approximately 50% of the sample concentration in
ug/L.
b) Spike 2 is approximately 100% of the sample concentration
in ug/L.
c) Spike 3 is approximately 150% of the sample concentration
in ug/L.
5) The data for each MSA analysis must be clearly identified in
the raw data documentation (using added concentration as the x-
variable and intensity or found concentration as the y»
variable) along with the slope, x:intercept, y-intercept and
correlation coefficient (r) for the least squares fit of the
data, the results must be reported on Form XI - LCIN. Reported
values obtained by MSA must be flagged on the data sheet (Form
I - LCIN) with the letter "S" if the correlation coefficient is
greater than or equal to 0.995.
6) If the correlation coefficient (r) for an MSA analysis is less
than 0.995, the MSA analysis must be repeated once. If the
correlation coefficient is still less than 0.995, report the
results on Form I - LCIN from the run with the greater
correlation coefficient "r" and flag the result with a "+". On
Form XI - LCIN report the results of both MSA analysis and flag
with a "+" for any MSA result that yields a correlation
coefficient less than 0.995.
E-16 10/91
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Figure 1
FURNACE ATOMIC ABSORPTION AND HYICP
ANALYSIS SCHEME
PREPARE AND ANALYZE
SAMPLE AND ONE SPIKE
30% THE LINEAR RANGE
(Double Exposures (injections)
Required)
ANALYSES WITHIN
CALIBRATION RANGE
YES
RECOVERY OF SPIKE
LESSTHAN40%
NO
SPIKE RECOVERY
LESS THAN 85% OR
GREATER THAN 115%
YES
QUANTITATE BY MSA WITH 3
SPIKES AT 50.100. & 150%
OF SAMPLE CONCENTRATTON
(Only Single Exposures
(injections) Required)
1
CORRELATION COEFFICIENT
LESS THAN 0.995
NO
FLAG DATA WITH "S"
NO
DILUTE SAMPLE
AND SPIKE
If YES, Repeat Only ONCE
If Still YES
NO
If YES, Repeat Only ONCE
If Still YES
FLAG DATA
WITH AN "E"
QUANITTATE FROM
CALIBRATION CURVE
AND REPORT DOWN
TOIDL
FLAG DATA
WITH A V
E-17
10/91
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