EPA-810/B-92-008
Untod Slam Office of Water (WH450) EPA 810-8-02-008
Environmental Protection Office of PertddM and February 1982
Agency Toadc Subatancee (H-7S01C)
QUALITY ASSURANCE PROJECT PLAN
FOR THE
NATIONAL PESTICIDE SURVEY OF DRINKING WATER WELLS
ANALYTICAL METHOD 9 • NITRATE AND NITRITE
Prepared by:
Julie Zalikowski
Montgomery Laboratories
555 East Walnut Street
Pasadena, California 91109
Prepared for:
U.S. Environmental Protection Agency
Technical Support Division
Office of Drinking Water
26 W. Martin Luther King Drive
Cincinnati, Ohio 45268
U S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12tn Moor
Chicago, IL 60604-3590
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Section No. 1 r
Revision No. 3
Date: August 30, 1990
Page 2 of 2
APPROVAL PAGE
U.S. Environmental Protection Agency Montgomery Laboratories
Project Officer Date Quality Assurance Date
TSD Quality Assurance Date Project Manager Date
Coordinator
TSD Technical Monitor Date Program Manager Date
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s .
l-f
v-)
Section No. 2
Revision No. 6
Date: April 30, 1990
Page 1 of 2
NATIONAL PESTICIDE SURVEY
QUALITY ASSURANCE PROJECT PLAN FOR
ANALYTICAL METHOD 9 - NITRATE AND NITRITE
2. TABLE OF CONTENTS
Section
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
TITLE AND APPROVAL PAGE
TABLE OF CONTENTS
PROJECT DESCRIPTION
PROJECT ORGANIZATION AND RESPONSIBILITIES
QUALITY ASSURANCE OBJECTIVES FOR
MEASUREMENT DATA
SAMPLING PROCEDURES
SAMPLE CUSTODY
CALIBRATION PROCEDURES AND FREQUENCY
ANALYTICAL PROCEDURES
DATA REDUCTION, VALIDATION REPORTING
INTERNAL QUALITY CONTROL CHECKS
PERFORMANCE AND SYSTEM AUDITS
PREVENTIVE MAINTENANCE
SPECIFIC PROCEDURES FOR ASSESSING
MEASUREMENT SYSTEM DATA
CORRECTIVE ACTION
Pages
2
2
1
4
1
3
5
2
2
2
2
1
1
t
2
Revisions Date
6
6
6
6
6
6
6
6
6
6
6
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6
6
6
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16. QUALITY ASSURANCE REPORTS TO
MANAGEMENT
4/30/90
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Section No 2
Revision No. 6
Date April 30, 1990
Page 2 of 2
2. TABLE OF CONTENTS (continued)
Appendices
A.
B.
C.
D.
E.
F.
G.
NPS METHOD 9
RFA METHODOLOGY
FORMAT FOR NPS DATA FILES
DIXON'S TEST
ROUNDING AND SIGNIFICANT FIGURES
NPSIS SAMPLE RECEIPT SOFTWARE FOR
LABORATORIES
DATA ARCHIVING SOP
Pages
8
8
5
5
3
17
4
Revisions
6
6
6
6
6
6
6
Date
4/30/90
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Section No 3
Revision No. 6
Date. April 30, 1990
Page 1 of 1
3. PROJECT DESCRIPTION
Project Summary
Montgomery Laboratories will provide analytical services to the U.S. EPA for analysis of samples
collected from well water sites throughout the country to assess the nature and scope of
contamination by pesticides and their by-products (National Pesticide Survey or NPS). These data will
be used to determine correlations between pesticide contamination and such factors as patterns of
pesticide usage and ground water vulnerability.
Methods
This QAPjP deals with Method 9 of the NPS. Montgomery Laboratories will also be performing
analyses using Methods 1 and 3 which are covered in another QAPjP.
NPS Method #9 - EPA Method 353.2 - Nitrates
Nitrates are determined by an automated cadmium reduction method which reduces
nitrate to nitrite which is then diazotized with sulfanilamide and coupled with
n-(l -naphthyl)-ethylenediamine dihydrochloride to form an azo dye which is
measured calorimetncally in a segmented flow system.
The sample is passed through a coil containing granulated preconditioned cadmium
to reduce nitrate to nitrite. The efficiency of the reduction column is verified using
N03 and NO2 solutions. Efficiency must be greater than 95% for analytical results
to be valid. The nitrite is determined by diazotizing with sulanilamide and coupling
with N-(1-Naphthyl)-ethylenediamine dihydrochloride to form a highly colored azo
dye which is measured calonmetrically using a continuous flow analyzer. Analysis is
performed at a rate of 30 to 70 samples per hour for the NPS project.
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Section No 4
Revision No 6
Date: April 30, 1990
Page 1 of 4
4. PROJECT ORGANIZATION AND RESPONSIBILITIES
The staff organization and chain of command which Montgomery Laboratories will utilize for this
project is shown in Exhibit 4.1. Details of staff responsibilities and qualifications are summarized in
this Section.
PROJECT MANAGER: ANDREW D. EATON, Ph.D
As Laboratory Director, Dr. Eaton will serve as the Project Manager and have full responsibility
and authority for the project and serve as liaison with the U.S. EPA Project Officer. Dr. Eaton will
review all of the final data generated for the project, oversee any major decisions which must be
made, insure that the Program Manager has the necessary resources to accomplish the proposed
work within the allotted time and budget, and insure that all laboratory and EPA specified quality
control guidelines are being performed and are acceptable. Dr. Eaton will also insure that appropriate
corrective action is taken for any out-of-control events that occur. Dr. Eaton can be reached at
Montgomery's telephone number: (818) 796-9141.
PROGRAM MANAGER: JULIE ZALIKOWSKI
Julie Zalikowski will serve as the Program Manager and provide daily technical and managerial
guidance to insure that the analytical work is performed within EPA specified turn-around times and
conforms with the quality control guidelines specified by EPA and this QA Project Plan. Julie can be
reached at Montgomery's telephone number: (818) 796-9141.
QUALITY ASSURANCE OFFICER: RICK A. MEALY
Mr. Mealy will insure that all contract specified and routine internal laboratory quality control
procedures are performed by the analysts for this project. He will also insure that all data and
supporting quality control parameters are reviewed and approved by an appropriate supervisor or
peer before the analyst is allowed to enter the data into the computer system. Approval is granted
upon verification that all quality control parameters lie within specified acceptance limits and no
analytical or computational errors appear on the analyst's data sheets. Mr Mealy can be reached at
Montgomery's telephone number: (818) 796-9141.
ASSISTANT QUALITY ASSURANCE OFFICER: WAVERLY BRAUNSTEIN
Ms. Braunstein will serve as the Assistant Quality Assurance Officer, performing periodic audits.
She is currently the laboratories' Assistant QAO.
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Section No 4
Revision No 6
Date: April 30. 1990
Page 2 of 4
EXHIBIT 4-1
MONTGOMERY LABS
NPS STAFF ORGANIZATION
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Section No. 4
Revision No. 6
Dale: April 30. 1990
Page 2 of 4
EXHIBIT 4-1
MONTGOMERY LABS
NFS STAFF ORGANIZATION
EPA Project Officer
Method 1 and 3
Robert Maxey
EPA Project Officer
Method 9
David Munch
Project Manager
Andrew Eaton, PhD
Laboratory Director
Quality Assurance
Rick Mealy
W. Braunstein
EPA Tech Monitor
Method 1 and 3
Robert Maxey
Program Manager
Julie Zalikowski
EPA Tech Monitor
Methods
Meianie Zuicker
Data handling and
reporting
Beverly Gaskins
Method 1
Franklin
Constantine
Method 9
Whitney Moore
Extractions
Rick Hansen
Stan KUckert
Suzette Urio
Glenn Okui
UsaLoring
Enrique Gomez
Francisco Gomez
Methods
Roobik Yaghoubi
Sample
Receiving
Beverly Gaskins
Bruce Havlik
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Section No 4
Revision No 6
Date: April 30, 1990
Page 3 of 4
NITRATE ANALYSIS: WHITNEY MOORE
Ms. Moore will perform analysis for Total Nitrate and Nitrite by modified EPA Method 353.2,(RFA,
Cadmium Reduction). Ms. Moore has three years of RFA experience at Montgomery Laboratories and
over five years of analytical experience.
SAMPLE RECEIVING CLERK
Beverly Gaskins will be the primary Sample Receiving Clerk. The backup Sample Receiving
Clerk will be Bruce Havlik, who is Montgomery Laboratories current Sample Receiving Clerk. Both can
be reached at Montgomery's phone number during working hours. Montgomery's address for sample
receipt is 555 E. Walnut, Pasadena, CA, 91101. The phone number is (818) 796-9141. Normal
working hours are from 8 am to 5 pm local Pacific time.
DATA HANDLING AND REPORTING CLERK
Beverly Gaskins will be the Data Handling and Reporting Clerk. This will be the same person
who will be primary contact for sample receipt. Julie Zalikowski will serve as backup.
TECHNICAL MONITOR: DAVID MUNCH
The EPA Technical Monitor for Method 9 is David Munch of EPA's TSD at Cincinnati. His
telephone number is (513) 569-7945. Mr. Munch will serve as primary contact for all technical matters
concerning Method 9.
EPA PROJECT OFFICER: DAVID MUNCH
The EPA Project Officer for Method 9 will be David Munch of the EPA's office in Cincinnati. His
telephone number is (513) 569-7945. Mr. Munch will serve as primary contact for all contractual
matters concerning Method 9.
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Section No 4
Revision No 6
Date- April 30, 1990
Page 4 of 4
SUMMARY
The following is a summary of the Montgomery Laboratories personnel assigned to this project
for Method 9:
Program Manager: Julie Zalikowski
QA Oversight: Rick Mealy
Waverly Braunstein
Sample Receipt: Beverly Gaskins
Bruce Havlik
Sample Analysis: Whitney Moore
Data Handling and Reporting: Beverly Gaskins
Backup: Julie Zalikowski
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Section No 5
Revision No 6
Date April 30. 1990
Page 1 of 1
5. QUALITY ASSURANCE OBJECTIVES FOR MEASUREMENT DATA
Initial Demonstration of Capabilities: Determining Reporting Limits
The following procedure will be used to determine the minimum reporting level (MRL).
1) Spike eight reagent water samples at .25 mg/l and analyze in a single day.
2) Compute Minimum Detectable Level (MDL) by multiplying the standard deviation by
the student's t value, appropriate for a 99% confidence level, and a standard
deviation estimated with n-1 degrees of freedom.
3) The calculated MDL must be less than .25 mg/l.
4) The determined MDL will be evaluated by the Technical Monitor, since the target
MDL is not included in the method.
5) The minimum reporting level (MRL) is computed as 3 times the approved MDL.
6) The lower concentration calibration standard must be prepared at a concentration
equal to the minimum reporting level.
Initial Demonstration of Precision and Accuracy Capabilities
1) Montgomery Laboratories will be required to demonstrate precision and accuracy
prior to the survey.
2) Five reagent water samples will be spiked at 10 times the MRL and analyzed. An
additional 15 samples will be spiked and analyzed, 5 on each of 3 days. The data
from these 20 spiked samples will be used to determine precision.
3) The relative standard deviation (RSD) must be less than or equal to 10%.
4) Outliers: Dixon's test will be used to determine outliers. There can be no more
than 3 outliers per analyte from the 20 spiked controls. The method for using
Dixon's test is included as Appendix D.
5) To determine accuracy, four aliquots of an EPA EMSL-CI Quality Control sample
with a true value close to 10 times the MRL concentration will be analyzed. The
mean recovery must lie within the 95% confidence interval given by EMSL for the
QC sample.
6) Data will be reported to the EPA Technical Monitor.
Miscellaneous Other QC Notes
1) The results of the Initial Demonstration of Capabilities will be reported to the
Technical Monitor for approval and inclusion into the NPS survey.
2) Additional samples will be collected at 10% of the samples sites for spiking at the
laboratory. The data from these spikes will be used to assess the recovery of the
analytes from a variety of matrices. These samples are to be spiked at analyte
concentrations equal to 2 or 10 times the reporting level or 10,000 ug/l. Samples
collected for the analyte stability studies are to be spiked at 10 times the minimum
reporting level for each analyte.
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Section No 6
Revision No. 6
Date April 30, 1990
Page 1 of 3
6. SAMPLING PROCEDURES
Sample bottle preparation, sample collection, and sample shipping will be performed by an EPA
contractor (ICF). Samples will be shipped iced for overnight delivery to the laboratory.
The containers, preservatives, and maximum holding times specified in the methods for each
analytical group required for this contract are listed in Table 6.1. Any work orders supplied by the
EPA with the samples are used as a packing slip by the Sample Receiving Clerk to insure that the
correct number of bottles have been shipped and have been correctly labelled. Table 6.2 lists the
number of bottles to be shipped to Montgomery with each sample type.
TABLE 6.1
SAMPLE CONTAINERS, PRESERVATIVES, AND HOLDING TIMES
ANALYSIS SIZE PRESERVATIVE HOLDING TIME
NPS #9 125 ml H2SO4 - 0.25 ml Analyze 28 Days
All samples will be stored at 4oC
Sampling Paperwork
A) Figure 6.1 is a copy of the label to be used on the sample bottles. The label will
contain the following information: Sample number, Sample code, Date sampled,
and Sampler name. The following codes will be used for the sample number
identification:
The example sample number is PD-0415-1-9-6.
P = National Pesticide Survey Sample
D = Domestic well (could be C = Community well)
0415 = Site number
1 = JMM Lab number
9 = Method number
6 = Bottle number
An additional code will be on each sample label. An example of this code is
JMM-#9-XXX, where JMM is Montgomery Laboratories, #9 is method 9, and XXX is
a code for the exact sample type. The following is a list of possible sample types
and their codes:
FS = Field Sample
FD = Field Duplicate
BU = Backup Sample
T/S = Time Storage, t = 14 days
T/SO = Time Storage dup , t = 0 days
T/S 14 = Time Storage dup, t = 14 days
LS = Laboratory Spike, where
LS-A1 = Lab spike, Mixture A, Level 1
B) the types of analyses to be performed for Method 9 are listed in Section 9 of this
Plan.
C) Appended is a copy of the field sample tracking sheet which will be used.
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Section No. 6
Revision No. 6
Date: April 30, 1990
Page 2 of 3
FIGURE 6.1
SAMPLE NFS LABEL
NATIONAL PESTICIDE SURVEY
SAMPLE #: PD-0415-1-9-6
JMM - METHOD* 9 KIT: 521
FIELD SAMPLE
PRESERVATIVE: H2SO4
DATE | TIME | SAMPLER
Legend: - R = resample
B = performance evaluation
Well type - D = domestic
C = commercial
Sample type identifier -
01 = field sample
03 = backup sample
04 = lab spike (A1)
06 = lab spike (A3)
Sample Number Explanation:
PD-0415-1-9-6
I! I! I I
I | | Sample Type Identifier
j | Method # (9)
II I Lab * (1)
|| Site #
! Well Type
NPS Designation
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Section No 6
Revision No 6
Date: April 30, 1990
Page 3 of 3
TABLE 6.2
TOTAL SAMPLE BOTTLES REQUIRED
Kit Type
Sample type
Bottle size
Method #
Primary
Backup
Lab Spike
T/S D14
Totals
# sites
TOTAL
JMM #1
Regular
1000 ml
1
1
1
2
825
1650
1000 ml
3
1
1
2
825
1650
125 ml
9
1
1
2
825
1650
JMM #2
Reg + LS.
1 000 ml
1
1
1
1
3
450
1350
1000 ml
3
1
1
1
3
150
1200
125 ml
9
1
1
1
3
150
1050
JMM #3
Reg _ L S -r T/S
1000 ml
1
1
1
2
6
225
1080
1000 ml
3
1
1
2
6
150
870
125 ml
9
1
1
2
6
75
660
TOTAL BOTTLE REQUIRED:
1000 ml = 7800
125ml = 3360
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Section No. 7
Revision No 6
Date: April 30, 1990
Page 1 of 5
7. SAMPLE CUSTODY
Laboratory Notification and Sample Receipt
The EPA sampling contractor (ICF) will supply the laboratory with a list of sites to be sampled
every two weeks. The laboratory will be kept up to date with any changes in sampling daily using the
software provided by EPA. A detailed explanation of the software is provided in Appendix F.
Upon receipt of the samples at the laboratory the Sample Receiving Clerk will inspect samples,
check the samples' pH with pH paper, and notify the sampling contractor if the sample pH is greater
than pH 3. The Sample Receiving Clerk will also notify the sampling contractor as to the condition of
the sample bottles, ice, and discrepancies between the sample labels and the paperwork. This
notification will take the form of computer modem contact with ICF's system. A detailed flowchart of
the notification process is included at the end of this chapter. If a problem is found, the Sample
Receiving Clerk will notify the Program Manager who will then notify the Technical Monitor.
Samples must arrive at the laboratory with ice still remaining in the shipping box. If a sample
box arrives at the laboratory without any ice remaining, the laboratory will contact the Technical
Monitor immediately.
Holding Times and Storage
Samples will be held in the dark and in the refrigerator at 4oC until analysis. Strict adherence to
sample maximum holding time of 28 day is required.
Time storage samples must be analyzed within plus or minus 4 days of the proper date. For
example, non-stored time storage samples must be spiked within the 28 day holding time for samples
and must be analyzed within 4 days of that spike. A stored time storage sample must be analyzed by
no sooner than 24 days and no later than 32 days after being spiked.
Sample status will be monitored daily by the Data Handling and Reporting Clerk and the
Program Manager. This monitoring will insure that the samples are extracted and analyzed within the
proper holding times. Items to be checked daily will include: 1) sample holding times to insure that
all analysis holding times are met; 2) completeness of data packages to insure that data will be
reported in the required amount of time; and 3) status of all outstanding QC problems.
Refrigerator and Freezer temperatures are monitored daily. The temperature at the beginning of
the day is recorded on the record sheet taped to the front of the unit. Acceptance limits for the
refrigerator are 2 to 8oC. Acceptance limits for the freezer are -30 to -10oC. A copy of this form may
be found at the back of this section.
Sample Disposal
Water samples for Method 9 will be disposed of after the 28 day holding time has been
exceeded.
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Section No 7
Revision No. 6
Date. April 30, 1990
Page 2 of 5
Sample kits will be returned to the EPA as soon as possible after the arrival of the samples. The
EPA will provide for the return shipping to either the EPA or the sampling contractor.
Sample Tracking
Sample tracking will be performed by the Data Handling and Reporting Clerk. As stated above,
when sample arrive they will be entered onto Sample Receipt Forms. This form contains all of the
information about sampling and shipping needed for the final sample report. ICF will supply much of
this information.
The laboratory will use the sample identification number described in Section 6 instead of
assigning the sample a laboratory tracking number. The primary means of tracking the samples will
be by analysis set number.
The Data Handling and Reporting Clerk will then assign each sample to an analysis set. The
sample information will then be entered onto the Sample Tracking Form. Each analysis set will be
assigned a unique number and will be tracked as a set. The number will be in the form #-•####
where the first number is the Method number (1, 3 or 9) and the other number is assigned
consecutively.
The Data Handling and Reporting Clerk and the Program Manager will monitor the status of all
sample analyses by examination of the Sample Tracking Forms. The Data Handling and Reporting
Clerk will check the status of the outstanding analyses daily by talking to the analysts involved. Any
potential problems will be brought to the attention of the Program Manager, who will then contact the
appropriate supervisors.
Copies of all of the tracking and reporting forms are included at the back of this section. This
includes not only the tracking forms but the data reporting forms.
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Section No. 7
Revision No. 6
Date: April 30. 1990
Page 3 of 5
Refrigerator
If
1C - >C
TTAJl
r«*
4
2_
»
1»
11
12_
13
14
IS
14
17
Iff
2j
22
21_
24
25
2<
»
11 L
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Section No. 7
Revision No. 6
Date: April 30. 1990
Page 4 of 5
SAMPLE TRACKING AND RESULTS FORM
METHOD 9
Analysis Set Number: 9 -
Analyzed By:
Date Analyzed: /_
Spiked Byt
Sample ID
[PD-
PC- -1-9-
PD-
PC- -1-9-
PD-
PC- -1-9-
PD-
PC- -1-9-
PD-
PC- -1-9-
PD-
PC- -1-9-
PD-
PC- -1-9-
PD-
PC- -1-9-
PD-
PC- -1-9-
PD-
PC- -1-9-
PD-
PC- -1-9-
fB-
PC- -1-9-
PB-
PC- -1-9-
PD-
PC- -1-9-
Pff-
PC- -1-9-
P5-
PC- -1-9-
PB-
PC- -1-9-
PB-
PC- -1-9-
PB-
PC- -1-9-
PB:
PC- -1-9-
PB-
PC- -1-9-
PB-
PC- -1-9-
PB-
PC- -1-9-
Oate Date
Saapled Spiked
Sample
Volume
Nitrate
Cone.
Comments
CoaMntsi
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Section No. 7
Revision No. 6
Date: April 30. 1990
Page 5 of 5
RFA Analysis
Anmivft
LCS Source
Ctl. Std. Source
Dale fl*v/*w*r Oaf*
Oat* Prepared Exolntlon Oar* True Acceptance Limit*
Oaf* Prepared Eiolrttlon Oar*
Corr. Catll. S/oo* fnrereepr
1
2
3
4
5
6
7
a
9
10
1 1
12
13
1 1
15
• 6
' 7
• 8
•9
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
SAMPLE
j»moi«
(mi.)
DILUTION
toni
(mltl
P»«K Htigni
'mm)
Calculates
(mg/L)
Rtoorito
fmg/L)
OK3ESTX3N
wcignt
(gmi)
total voium*
"fltti
R*ooft*a
__[_mg/ng)
COMMENTS
•PNTaTO
Samoi*
i
2
3
4
Ong. Cone.
A (mg/L)
Total Vol.
T (mL)
Spill* Volum*
3 (mL)
Sok» Cone.
C (mart.)
Final Cone.
6 (mg/L)
F . % Rccovwv
(ET-AIT-Bl) X 10
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Section No 8
Revision No 6
Date April 30, 1990
Page 1 of 2
8. CALIBRATION PROCEDURES AND FREQUENCY
Calibration Solutions
Montgomery will furnish the stock standards for Method 9. Separate dilutions will be made from
these stocks for the calibration standards and the solutions for spiking samples. Each time that new
calibration standard dilutions are prepared they must be compared to the existing calibration curve,
and the observed concentration must agree within plus or minus 5% of the expected concentration.
Records shall be kept in the stock standard notebook indicating how, when, and by whom the
dilutions were made. Each standard dilution will be assigned a standard number. This number will
be recorded with all sample sets analyzed with this standard dilution to provide traceability for the
standard used on any given analytical run. This will be the method of tracking each new standard
dilution and stock solutions. The Standards Tracking form is included at the end of this section.
The Standard numbers will be assigned as per the following code: NPS#-001-P##-1; where
NPS# is the NPS method number, 001 is the number of the stock standards given to ML by the EPA,
P## is the standards notebook page number which describes the preparation of the standard mix
preparation, and 1 is the level of the dilution (1=low, 2=medium, and 3=high). The following
example, NPS9-009-P12-3, refers to NPS9-009 or the ninth stock standard shipped from the EPA.
NPS9-009-P12 is a cocktail prepared on page 12 of the standards notebook, and NPS3-009-P12-3 is a
high level standard prepared from cocktail NPS9-009-P12.
Holding times for the standards are not specified for the standards but our laboratory has found
the nitrate stock standard to be stable for 6 months to one year. Secondary standard dilutions will be
prepared monthly and the working calibration standard will be prepared daily. Standards will be
stored in a different refrigerator from the samples at 4°C.
Calibration Curve
Detailed calibration procedures are not provided in the method. Montgomery utilizes 7
calibration standards at the beginning and end of each autosampler run. The lowest standard must
be at the MRL and the others should correspond to the range of concentrations expected in the
samples. The standards go from 0.3 to 10.0 mg/l The initial calibration must be linear with a
correlation coefficient of at least 0.996 and is the calibration on which sample quantitation is usually
based. The calibration at the end of the run is performed as a backup calibration in case of problems
during the run and to verify lack of significant instrument drift.
All calibration curves will be filed along with the analysis set.
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Section No 8
Revision No 6
Date- April 30. 1990
Page 2 of 2
Daily System Checks
An EMSL-QC sample provided by EPA/Cincinnati must be run every sample set to check the
standard curve. The results must be within the 95% confidence interval given for the QC sample.
The efficiency of the reduction column must be verified daily using nitrate and nitrite solutions.
The efficiency must be greater than 95% for the analytical results to be valid.
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Section No 9
Revision No 6
Date April 30. 1990
Page 1 of 2
9. ANALYTICAL PROCEDURES
This QAPjP deals with Method 9 of the NPS only. The detailed method is attached to this
QAPjP as Appendix B.
Method Summary
NPS Method 9 is based on EPA Method 353.2 for Nitrate-Nitrite which is attached in Appendix
A. Nitrates are determined by an automated, cadmium reduction method which reduces nitrate to
nitrite which is then diazotized with sulfanilamide and coupled with n-(l-naphthyl)-ethylenediamme
dihydrochloride to form an azo dye which is measured calorimetncally in a segmented flow system.
There is no confirmation planned for nitrates.
Equipment
Primary Rapid Flow Analyzer
ALPKEM RFA 300
Dual Channel System
Dual flow-through photometers
Autosampler
Cadmium manifold
Dual channel strip chart recorder
Backup Continuous Flow Analyzers
Orion Scientific CFA2000
Dual Channel System
Dual flow through calorimeters
Modified AAII autosamplers
Cadmium reduction manifold
Dual channel strip chart recorder
A/D convenor for use with data system
Analysis Types
The following table is a list of the analysis types and frequency of analysis for Method 9.
Analysis Type Frequency
Method Blank 1/Set
Calibration Standards (7+7) 14/Set
Column efficiency check 1/Set
EMSL Check sample 1/10 Field Samples
Field Sample 1/Site
Backup Sample As Needed
Spiked Sample 10%
Duplicate Day 0 time Storage Samples 10%
Duplicate Day 14 Time Storage Samples 10%
Performance Evaluation Samples As Requested
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Section No 9
Revision No 6
Date. April 30, 1990
Page 2 of 2
Maximum Number of Samples Per Set
Based on the required QC, the maximum number of field samples which could be analyzed per
sample set is in excess of 100. Note that each "sample set" is defined as all samples, blanks, spiked
samples, etc., which are analyzed by the same person in a 12 hour period.
Method Deviations
The method attached to this QAPJP as Appendix A deviates from 352.2 by using an imidazole
buffer to eliminate many metallic interferences. This buffer is different from that specified in 353.2.
This deviation was approved by the Technical Monitor.
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Section No 10
Revision No 6
Date. April 30, 1990
Page 1 of 2
10. DATA REDUCTION, VALIDATION AND REPORTING
Data Reduction
All data for the Method 9 will be collected on strip charts. Data calculation is based on linear
regression of the standard peak heights. The program automatically plots linear regression results
and confidence intervals.
The rounding of numbers and significant figures, as consistent with the NPS reporting format, is
addressed in Appendix E. This Appendix was taken from Chapter 7 of EPA publication
EPA-600/4-79-019, "Handbook for Analytical Quality Control in Water and Wastewater Laboratories."
Data Verification
The data will be reviewed and checked by the primary analyst. The primary analyst will review
all of the raw data and calculation and insure that the QC criteria was met. Following completion of
each analysis set, the analytical raw data, RFA runs, and QC summary sheets are reviewed by a peer
analyst. The completed data and QC are then submitted to the NPS project Data Handling and
Reporting Clerk and the Program Manager to verify that all quality control parameters fall within
acceptance limits and to review the analytical data for calculation errors or inconsistencies. The Data
Handling and Reporting Clerk will then enter the data into the computer data system.
The following items are to be checked for each sample set:
1) Is the date from sampling to receipt within the limits set by the survey requirement
(1 day)? Was ice present in the sample shipping container upon receipt?
2) Is the date from sampling to analysis within the limits set by the survey requirements
(28 days)?
3) Is the concentration of a blank equal to or greater than one-half of the MRL?
4) Is the concentration of a field sample above the MRL?
5) Is the concentration of nitrate in the quality control sample within the limits set by
EPA? '
6) Are the dates for the Time Storage Samples correct? Were they spiked and
analyzed within the correct dates?
Data Validation
Validation of analytical data is dependent on insuring that key procedural steps which impact
data quality are followed and that all quality control parameters fall within documented acceptance
criteria. The following procedural steps must be adhered to for all of the NPS methods since
deviations can have a serious impact on data quality.
After analysis of a high concentration sample, a reagent water blank should be run
until there is no longer a memory effect.
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Section No. 10
Revision No 6
Date- April 30. 1990
Page 2 of 2
Instrument performance must be checked daily and routine and special
maintenance must be documented in the instrument maintenance log.
Samples must be warmed to room temperature before performing analysis.
All laboratory analysts go through an orientation and training program to insure that they are
performing all of the required steps and quality control parameters for their analysis. Training is
provided by the appropriate senior analyst and verification of proper training is provided by not
allowing the analyst to work on samples until performing acceptably on EPA performance samples
which are provided to the analyst by the QA Officer as single blind samples. Once an analyst is
trained, his work is continually reviewed by his immediate supervisor and the Manager of Analytical
Services. His/her work is always sporadically reviewed by the QA Officer through review of
performance on periodic double blind check samples and routine laboratory system audits
Data Reporting
All data will be reported as sample sets. A copy of the data reporting forms is included in
Section 7 of this QAPjP. A sample set is defined as all samples, blanks, spiked samples, etc., which
are analyzed by the same person within a 12 hour period. When the sample set is completed, an
ACSII file in the required format will be produced. A copy of the required format is provided as
Appendix C. All data for a sample set are to be reported as a complete data set, including all QC
data no later than two months from the date of sample collection. The data files will be sent to
Christopher Frebis at the EPA in Cincinnati, Ohio. The files will be on IBM compatible 5.25 inch floppy
disks.
Fast Track reporting will be required for all samples >10 mgr/L for nitrate. Fast Track reporting
means that the Technical Monitor will be called immediately and the phone call will be followed up
immediately with written notification.
Storage of Data
All laboratory data and information pertaining to NPS will be stored for the duration of the
program. This includes all autoanalyzer runs, instrument logs, reagents and standard preparation
records, calibration data, and data and records related to corrective actions. All data will be stored in
files labeled with the sample set number for the method. A master log will be kept of all samples with
reference to the sample set it was analyzed with. All data will be kept in hardcopy form. All data will
be stored in locked file cabinets. Only the Program Manager, Data Tracking and Reporting clerk and
QA Officer will have keys to the data. Appendix G contains the Montgomery Archiving SOP.
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Section No 11
Revision No 6
Date' April 30, 1990
Page 1 of 2
11. INTERNAL QUALITY CONTROL CHECKS
This section lists the type and frequency of quality control checks to be done in conjunction with
this project. Any time a QC sample falls outside the acceptance criteria an "out-of-control" situation
exists. A corrective action form must be filled out stating the appropriate information (Section 15).
The Program Manager must be informed and no further samples analyzed until the system is shown
to be back in control. Data produced while the system is out-of-control are unacceptable and cannot
be used for any purpose. It is imperative that the QC discussed here is followed and the QC results
thoroughly documented.
Frequency of QC Samples
The following table lists the frequency of field and QC samples to be analyzed for Method 9.
Analysis Type Frequency
Method Blank 1/Set
Calibration Standards (7&7) 14/Set
Performance Evaluation Samples As Requested
. EMSL-QC standards 1 /10 Samples
Column Efficiency Check 1/Set
Laboratory QC Requirements For Analyses
1) A set of samples is defined as all samples, blanks, spiked samples, etc. which are
analyzed by the same person within a 12 hour period.
2) The measurement system is to be evaluated whenever any analyte is observed in a
method blank, at a concentration greater than or equal to one-half the MRL.
Method blanks are to analyzed with each sample set.
3) Time storage samples must be analyzed within plus or minus 4 days of the proper
date. For example, non-stored time storage samples must be spiked within the 28
day holding time for samples and must be analyzed within 4 days of that spike. A
stored time storage sample must be analyzed by no sooner than 24 days and no
later than 32 days after being spiked.
4) The requirement for monitoring calibration standard responses will be followed as
written in Section 8 of this QAPjP.
5) An EMSL-QC sample must be run every sample set to check the standard curve.
The results must be within the 95% confidence interval given for the QC sample.
6) The efficiency of the reduction column must be verified daily using nitrate and nitrite
solutions. The efficiency must be greater than 95% for the analytical results to be
valid.
7) Samples failing any QC criteria must be reanalyzed at the contractors expense.
8) Each time that new calibration standard dilutions are prepared they must be
compared to the existing calibration curve, and the observed concentration must
agree within plus or minus 5% of the expected concentration.
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Section No. 11
Revision No 6
Date: April 30. 1990
Page 2 of 2
9) Any deviation from the analytical procedures or QC requirements must be approved
by the Technical Monitor and documented in writing.
Miscellaneous Other QC Notes
1) Additional samples will be collected at 10% of the samples sites for spiking at the
laboratory. The data from these spikes will be used to assess the recovery of the
analytes from a variety of matrices. These samples are to be spiked at analyte
concentrations equal to 2 or 10 times the MRL, 10,000 ug/l. Samples collected for
the analyte stability studies are to be spiked at 10 times the minimum reportable
level for each analyte.
(After analysis of a high concentration sample, a reagent water blank should be
run.)
2) Instrument performance must be checked daily and routine and special
maintenance must be documented in the instrument maintenance log.
3) Samples must be warmed to room temperature before performing analysis.
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Section No 12
Revision No 6
Date April 30, 1990
Page 1 of 1
12. PERFORMANCE AND SYSTEM AUDITS
Performance and System Audits
The Quality Assurance Officer will review this QAPjP with all personnel associated with this
project to insure that they have read and understand it. Each analyst will sign a statement saying that
they have read and understand the QAPjP and will conduct the analyses in accordance with it. The
QA Officer or his assistant will conduct monthly system audits during which they will track a single
sample set throughout the system to insure that the Project Plan is being carried out. These system
audits will not be announced to the analytical staff prior to their being carried out. The analytical staff
is expected to cooperate-fully with the QA Officer during the audit. Any deficiencies will be reported
immediately to the Program Manager, the Laboratory Director, the analyst's supervisor, and the
Technical Monitor. A corrective action form will be filled out for each deficiency. The QC auditor
verifies that the deficiency has been corrected during the next audit. The frequency of system audits
will be increased if the frequency of QC problems increase.
A system audit will consist of tracking at least one sample set through every step of analysis
and reporting. All steps in the system will be evaluated, even if the sample set did not require their
use. For example, the maintenance logs will be checked during each audit, even if they were not
needed for this sample set. The content of the system audit will include (but not be limited to):
Sample receipt and recordkeepmg
Analysis set assignment
Sample holding times
LCS and spike assignment
Standards preparation and recordkeeping
Random calculation checks
Check analysis forms for completeness
Instrumental log books
Instrument calibration
Method Blank Results
Laboratory Spike sample results
Internal QC sample results
Corrective action reports and followup
Reports to Management
Timeliness of reporting QC problems
Other QC related matters
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Section No 13
Revision No 6
Date April 30. 1990
Page 1 of 1
13. PREVENTIVE MAINTENANCE
RFA Analyses
Routine maintenance will be performed on the rapid flow analyzer systems in accordance with
the following schedule:
Task Frequency
Clean lens on photometer Monthly or as required
Replace pump tubing As required by performance
Clean photometer flow cell Monthly or as required
Replace dialyzer membrane As required by performance
The laboratory performs all preventative maintenance inhouse.
The laboratory maintains a stock of critical spare parts and also has backup calorimeters, a
backup pump, and a backup autosampler for the CFA if the RFA system requires servicing since we
maintain two separate systems. The following list of replacement and consumable spares is
maintained within the laboratory at all times:
1) tubing-all sizes
2) mixing coils
3) autosampler cups
4) spare cadmium coil
6) flow cells
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Section No 14
Revision No 6
Date April 30, 1990
Page 1 of 1
14. SPECIFIC PROCEDURES FOR ASSESSING MEASUREMENT SYSTEM DATA
The following formulas are used to calculate the data for the QC checks and for statistics related
to QC checks.
Percent Recovery (R,)
For QC sample or spiked sample with non-spiked value < 1/2 MRL:
(100 * Final Concentration * Total Volume)
Percent Recovery (Ri) = - -
Spike Concentration * Spike Volume
For spiked sample with non-spiked sample value greater than or equal to 1/2 MRL:
(100 * [(Final Concentration * Total Volume) -
(original concentration * (Total Volume - Spike Volume)
Percent Recovery (Ri) = -— — - •
Spike Concentration * Spike Volume
Standard Deviation (Sr)
n 2
Standard Deviation (Sr) = ( S R? - R )
i = 1
n-1
where n = number of measurements for each analyte
R( = individual percent recovery value
R = average percent recovery value
Relative Standard Deviation (BSD)
RSD = (Sr/R) * 100
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Section No 15
Revision No 6
Date April 30. 1990
Page 1 of 2
15. CORRECTIVE ACTION
Corrective action is required in response to an out-of-control event. Out-of-control events are
signalled whenever a quality control sample or parameter falls outside of acceptance limits. The
specific out-of-control events are listed in Section 11 of this QAPjP. Quality control parameters are
evaluated for their acceptability on a daily basis according to the established acceptance limits and
are monitored with control charts to detect trends in accuracy and variability which are indicative of a
shift in the methodology caused by analytical error. The required frequency and acceptance limits for
these parameters have been discussed in other sections of this plan. The exact corrective actions are
also discussed in Section 11 of this QAPjP.
Any time a QC problem occurs the QC Officer, Program Manager and Sample Tracking and
Reporting Clerk must be informed. If the problem is serious or cannot be quickly resolved the
Technical Monitor will be informed. If the problem is analytical, the supervisor of the section will also
be informed.
The analyst or sample receipt clerk is the first to be aware when a QC parameter falls outside of
the acceptance limits and has primary responsibility for notifying the QC Officer and the Program
Manager and attempting to solve the problem. The analyst must keep the QC Officer and the Project
Manager informed of specifically which QC parameter(s) were unacceptable and what area the analyst
feels is the probable source of error. The method of notification will usually be by corrective action
form. The analyst and the Program Manager then map out a strategy of diagnostic tests to verify
whether this assessment is correct. It will be the responsibility of the Program Manager to insure that
the QA problem was solved prior to sample analysis proceeding.
The corrective action form will include the following information:
Date of out-of-control event
Problem
Action taken to correct problem
Verification that the problem was solved
Identification of sample set affected
Identification of sample set analyzed before problem was observed
The corrective action form will be submitted to the QA Officer, Data Handling and Reporting
Clerk, and the Program Manager. This information is included in the monthly progress reports
submitted to the Technical Monitor (see Section 16 of this QAPjP).
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Section No. 15
Revision No. 6
Date: April 30. 1990
Page 2 of 2
CORRECTIVE ACTION REPORT
CORRECTIVE ACTION REPORT
General Information:
Analysis Date: Analysis:
Extraction Datt: Matrix:
Analyst: Instrument ID:
Environmental samples impacted (ClientyjMM ID):
Brief description of the non-conformance: iCoiwms 1.2 & If
Actions taken to resolve the non-conformance: iCoiumn
Conclusions/Disposition of the data: /Coin™ it
Analyst _^_^_________
_ Da£.
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Section No 16
Revision No. 6
Date April 30, 1990
Page 1 of 1
16. QUALITY ASSURANCE REPORTS TO MANAGEMENT
Each day the Program Manager will meet with the Data Handling and Reporting Clerk to discuss
the status of all samples sets. This will include the status of shipping, analysis, QC, data reporting
and sample disposal. If needed, the Program Manager will discuss problems with the Laboratory
Director, the Quality Assurance Officer and other Laboratory Managers. These problems could include
QC problems, turnaround time problems, missing data problems, and personnel problems. It is our
intention that these daily meetings will be able to keep all of these problems under control before they
can seriously affect the overall project.
Monthly Report Format
Six copies of the monthly report are to be provided within 15 calendar days after the end of the
period being reported. The copies are to be sent to the appropriate Technical Monitor. The report
will be prepared by the Sample Tracking and Reporting Clerk and the Program Manager. The report
will be reviewed by the Project Manager and the QC Officer and signed off by the Project Manager
and Program Manager. .
The report format should contain the following information for the report period:
• Summary of progress
samples, received, analyses in progress
status of data processing for analyzed sets of samples
• Reports on standards
new dilutions and results of check before using
Summary list of bench-level corrective actions
• Identification of problems about any phase of the project
Copies of representative and unusual strip charts
Results of checks on column efficiency with a nitrate standard of the same
concentration as a nitrate standard.
Information requested by the Technical Monitor because of specific methodology or
problems encountered
Changes in any personnel working on the project
• Results of in-house system audits
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Appendix A
Revision No. 6
Date. April 30. 1990
Page 1 of 8
APPENDIX A
NPS METHOD 9
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NITROGEN, NITRATE-NITRITE
Method 353.2 (Colorimetric, Automated, Cadmium Reduction)
STORET NO. Total 00630
1. Scope and Application
1.1 This method pertains to the determination of nitnte singly, or nitnte and nitrate
combined in surface and saline waters, and domestic and industrial wastes. The
applicable range of this method is 0.05 to 10.0 mg/1 nitrate-nitrite nitrogen. The range
may be extended with sample dilution.
2. Summary of Method
2.1 A Altered sample is passed through a column containing granulated copper-cadmium to
reduce nitrate to nitnte. The nitnte (that ongmally present plus reduced nitrate) is
determined by diazotizmg with sulfamlamide and coupling with N-(l-naphtnyl)-
ethylenediamme dihydrochlonde to form a highly colored azo dye which is measured
colonmetncaily. Separate, rather than combined nitrate-mtnte, vaJues are readily
obtained by carrying out the procedure first with, and then without, the Cu-Cd reduction
step.
3. Sample Handling and Preservation
3.1 Analysis should be made as soon as possible. If analysis can be made within 24 hours, the
sample should be preserved by refrigeration at 4*C. When samples must be stored for
more than 24 hours, they should be preserved with sulfunc acid (2 ml cone. H2SO, per
liter) and refrigeration.
Caution: Samples for reduction column must not be preserved with mercuric chlonde.
4 Interferences
4.1 Build up of suspended matter in the reduction column will restrict sample flow. Since
nitrate-nitrogen is found in a soluble state, the sample may be pre-filtered.
4 2 Low results might be obtained for samples that contain high concentrations of iron,
copper or other metals. EDTA is added to the samples to eliminate this interference.
43 Samples that contain large concentrations of oil and grease will coat the surface of the
cadmium. This interference is eliminated by pre-extracting the sample with an organic
solvent.
5. Apparatus
5.1 Techmcon AutoAnaiyzer (AAl or AAII) consisting of the following components:
5.1.1 Sampler.
5.1.2 Manifold (AAI) or analytical cartridge (AAII).
5.1.3 Proportioning Pump
5.1.4 Colorimeter equipped with a 15 mm or 50 mm tubular flow ceil and 540 nm niters.
5.1.5 Recorder.
Approved for NPDES and SDWA
Issued 1971
Editorial revision 1974 and 1978
353.2-1
-------
5.1.6 Digital pnntcr for AAII (Optional).
6. Reagents
6.1 Cranulju-dtadmium: 40-60 mesh (MCB Reagents).
6.2 Copper-cadmium.- The cadmium granules (new or used) are cleaned with dilute HC1
(6.7) and coppenzed with 2% solution of copper sulfate (6.8) m the following manner:
6 2.1 Wash the cadmium with HC1 (6.7) and nnse with distilled water. The color of the
cadmium so treated should be silver.
6.2.2 Swirl 10 g cadmium in 100 ml portions of 2% solution of copper sulfate (6.8) for
five minutes or until blue color partially fades, decant and repeat with fresh copper
sulfate until a brown colloidal precipitate forms.
6.2.3 Wash the cadmium-copper with distilled water (at least 10 times) to remove all the
precipitated copper. The color of the cadmium so treated should be black.
6.3 Preparation of reduction column AAJ. The reduction column is an 8 by 50 mm glass tube
with the ends reduced in diameter to permit insertion into the system. Copper-cadmium
granules (6.2) are placed in the column between glass wool plugs. The packed reduction
column is placed in an up-flow 20* incline to minimize channeling. See Figure I.
6.4 Preparation of reduction column AAII: The reduction column is a U-shaped, 35 cm
length, 2 mm I.D. glass tube (Note 1). Fill the reduction column with distilled water to
prevent entrapment of air bubbles dunng the filling operations. Transfer the copper-
cadmium granules (6.2) to the reduction column and place a glass wool plug in each end.
To prevent entrapment of air bubbles in the reduction column be sure that all pump tubes
are filled with reagents before putting the column into the analytical system.
NOTE 1: A 0.081 I.D. pump tube (purple) can be used in place of the 2 mm glass tube.
6.S Distilled water: Because of possible contamination, this should be prepared by passage
through an ion exchange column composed of a mixture of both strongly acidic-cation
and strongly basic-anion exchange, resins. The regeneration of the ion exchange column
should be earned out according to the manufacturer's instructions.
6.6 Color reagent: To approximately 800 ml of distilled water, add, while stirring, 100 ml
cone, phosphoric acid. 40 g sulfanilamide. and 2 g N-l-naphthylethylenediamme
dthydrochlonde. Stir until dissolved and dilute to I liter. Store in brown bottle and keep
in the dark when not in use. This solution is stable for several months.
6.7 Dilute hydrochloric acid, 6N: Dilute 50 ml of cone. HC1 to 100 ml with distilled water.
6.8 Copper sulfate solution, 2%: Dissolve 20 g of CuSO.»5H,O in 500 ml of distilled water
and dilute to 1 liter.
6.9 Wash solution: Use distilled water for unpreserved samples. For samples preserved with
HjSO., use 2 ml H2SO, per liter of wash water.
6.10 Ammonium chloride-EDTA solution: Dissolve 85 g of reagent grade ammonium
chloride and 0.1 g of disodium ethylenediamme tetracetate in 900 ml of distilled water.
Adjust the pH to 8.5 with cone, ammonium hydroxide and dilute to I liter Add \/1 ml
Bnj-35 (available from Techmcon Corporation).
353.2-2
-------
INDENTATIONS FOR
SUPPORTING CATALYST
Cd TURNINGS
GLASS WOOL
TILT COLUMN TO 20° POSTION
FIGURE 1. COPPER CADMIUM REDUCTION COLUMN
(I 1/2 ACTUAL SIZE)
353.20
-------
6.11 Stock nitrate solution: Dissolve 7.218 g KNO, and dilute to I liter in a volumetric flask
with distilled water Preserve with 2 ml of chloroform per liter Solution is stable for 6
months. I ml = I 0 mg NO,-N.
6 12 Stock nitrite solution Dissolve 6 072 g KNO: in 500ml of distilled water and dilute to I
liter in a volumetric flask. Preserve with 2 ml of chloroform and keep under refrigeration
I Oml = 1 OmgNO:-N
6.13 Standard nitrate solution Dilute 10.0 ml of stock nitrate solution (6.1 l)to 1000 ml.
1 0 ml = OOlmgNO.-N Preserve wuh 2 ml of chloroform per liter Solution is stable
for 6 months.
6.14 Standard nitrite solution. Dilute 10.0 ml of stock nitnte (6.12) solution to 1000 ml.
1.0 ml = 0.01 mg NO:-N. Solution is unstable; prepare as required.
6.15 Using standard nitrate solution (6.13), prepare the following standards in 100.0 ml
volumetric flasks. At least one nitrite standard should be compared to a nitrate standard
at the same concentration to verify the efficiency of the reduction column.
Cone. mgNO:-N or VO,-N/1
0.0
0.05
0.10
0.20
0.50
1.00
2.00
400
6.00
ml Standard Solution/100 ml
0
0.5
1.0
2.0
5.0
10.0
20.0
40.0
60.0
NOTE 2: When the samples to be analyzed are saline waters. Substitute Ocean Water
(SOW) should be used for preparing the standards: otherwise, distilled water is used. A
tabulation of SOW composition follows;
Nad - 2453 g/1
CaCl- - 1 16 g/1
KBr - 0.10 g/1
NaF - 0.003 g/1
MgCl- - 5 20 g/1
KC1 - 0 70 g/1
H,BO, - 0.03 g/1
Na.SO, - 4 09 g/1
NaHCO, - 0 20 g/1
SrCl, - 0.03 g/1
Procedure
7 1
If the pH of the sample is below 5 or above 9, adjust to bet ween 5 and 9 with either cone
HClorconc. NH4OH.
72 Set up the manifold as shown in Figure 2 (AAI) or Figure 3 (AAII). Note that reductant
column should be in 20* incline position (AAI). Care should be taken not to introduce air
into reduction column on the A AII.
73 Allow both colorimeter and recorder to warm up for 50 minutes. Obtain a stable baseline
with all reagents, feeding distilled water through the sample line.
NOTE 3: Condition column by running 1 mg/1 standard for 10 minutes if a new
reduction column is being used. Subsequently wash the column with reagents for 20
minutes.
353.2-4
-------
9.
7.4 Place appropnate nitrate and/or nitnte standards in sampler in order of decreasing
concentration of nitrogen. Complete loading of sampler tray with unknown samples.
7.5 For the AAI system, sample at a rate of 30/hr. 1:1. For the AAII. use a 40/hr. 41 cam
and a common wash.
7 6 Switch sample line to sampler and start analysis.
Calculations
8.1 Prepare appropnate standard curve or curves derived from processing NO: and/or NO,
standards through manifold. Compute concentration of samples by comparing sample
peak heights with standard curve.
Precision and Accuracy
9.1 Three laboratories participating in an EPA Method Study, analyzed four natural water
samples containing exact increments of inorganic nitrate, with the following results:
Increment as
Nitrate Nitrogen
mg N/liter
029
0.35
2.31
2.48
Precision as
Standard Deviation
mg N/liter
0.012
0092
0.318
0.176
Accuracy as
Bias,
4- 5.75
-18 10
4- 4.47
- 2.69
Bias,
mg N/liter
-t-0.017
^0.063
-(-0.103
-0.067
Bibliography
1. Fiore. J., and O'Brien, J. E., "Automation in Sanitary Chemistry - parts 1 & 2 Determination
of Nitrates and Nitrites", Wastes Engineering 33, 1284238(1962).
2. Armstrong, F. A., Stearns, C. R., and Strickland, J. D., "The Measurement of UpwelJing and
Subsequent Biological Processes by Means of the Technicon AutoAnalyzer and Associated
Equipment", Deep Sea Research 14, p 381-389 (1967).
3. Annual Book of ASTM Standards. Part 31, "Water", Standard D1254, p 366(1976).
4. Chemical Analyses for Water Quality Manual. Department of the Interior. FWPCA. R. A.
Taft Sanitary Engineering Center Training Program. Cincinnati, Ohio 45226 (January, 1966)
5. Annual Book of ASTM Standards. Pan 31, "Water", Standard D 1141-75, Substitute Ocean
Water, p 48 (1976).
353.2-5
-------
"r*
25 s-
X _ ~
CSI
C9
353 :-
-------
CD
35J 2-7
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Appendix 8
Revision No 6
Date: April 30, 1990
Page 1 of 8
APPENDIX B
RFA METHODOLOGY
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Appendix B
Revision No 6
Date April 30, 1990
Page 2 of 8
APPENDIX B
RFA METHODOLOGY
RFATM METHODOLOGY®
ALPKEM Corporation
Summary of Method
Nitrate is reduced quantitatively to nitrite by cadmium metal in the form of an open tubular
cadmium reactor (OTCR). The nitrite thus formed plus any originally present in the sample is
determined as an azo dye (absorbance maximum, 543nm) following its diazontization with
sulfanilamide and subsequent coupling with N- 1-Naphthylethylenediamine(1). These reactions are
effected in acidic (1.0 pH 2.0) solution. Nydahl (2) provides a good discussion of nitrate reduction by
cadmium metal, while the specific details of OTCR's are given by Patton (3). Information concerning
mechanisms and kinetics of the color forming reactions can be found in references 4 and 5.
Interferences
The imidazole buffer eliminates interferences from iron, copper, or other metals. Turbid samples
should be filtered before determination. Samples with background absorbance at the analytical
wavelength may interfere.
Sample Handling and Preservation
Unpreserved samples must be refrigerated and determined within 48 hours. Preserve samples
with 2mL of concentrated sulfuric acid per liter of sample and store them at 4 degrees C. The holding
time for preserved samples is 28 days (2).
Reagents (3)
Stock Imidazole buffer, 0.1M (1L)
Imidazole 6.81 g
C3H4N2 (FW 68.08)
Hydrochloric Acid as required
HC1, concentrated
Deionized Water
Insert a pH electrode and a magnetic stirring bar into approximately 900mL of deionized water
contained in a 1 L beaker. Position the beaker on a magnetic stirrer. Turn on the stirrer and dissolve
6.81 g of imidazole in the deionized water. Adjust the pH of the solution to pH 7.5 with concentrated
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Appendix B
Revision No 6
Date- April 30, 1990
Page 3 of 8
hydrochloric acid. Transfer the solution to a 1L volumetric flask and dilute it to the mark with
deionized water. Mix well. Store the buffer in a tightly sealed bottle.
Cupnc Sulfate, 0.01 M (1L)
CuSO4.5H2O (FW 249.69)
Cupric Sulfate, 0.01 M (1L) 2.5 g
CuS04.5H20 (FW 249.69)
Deionized Water
Dissolve 2.5 g of cupric sulfate in approximately 900mL of deionized water contained in a 1L
volumetric flask. Dilute the solution to the mark with deionized water and mix it well. Store the
solution in a tightly sealed bottle at room temperature. The cupric sulfated solution is stable
indefinitely.
Working Imidazole Buffer
Stock Imidazole Buffer 50mL
Deionized Water 50mL
Cupric Sulfate, 0.01 M 100 uL
Brij-35R (30% w/v) 1 ml
Mix together 50mL of stock imidazole buffer, 50ml_ of deionized water, 100uL of 0.01 M cupric
sulfate, and 1mL of Brij-35. Prepare the amount of working buffer needed for the day's run.
Stock Sulfanilamide (SAN) (1L)
SulfanilamidlO.O g 10.0g
H2NC6H4SO2NH2 (FW 172.21)
Hydrochloric Acid 100mL
HC1, concentrated
Deionized Water
Cautiously add 100mL of hydrochloric acid to approximately 700mL of deionized water
contained in a 1L volumetric flask. Dissolve 10 g of sulfanilamide in the acidic solution. Dilute the
solution to the mark with deionized water and mix it well. The solution may be stored in a tightly
sealed bottle either at room temperature or refrigerated at 2-6 degrees C.
Working SAN
Stock SAN 50mL
-------
Appendix B
Revision No. 6
Date April 30. 1990
Page 4 of 8
Brij-35 0.5ml
Mix together 50mL of SAN and O.SmL of Brij-35. Prepare the amount of SAN needed for the
day's run.
N-(1-Naphthyl)ethylenediamine Dihydrochlonde (NED) (1L)
N-(1-Naphthyl)ethylenediamine Dihydrochloride 1.0 g
C10H7NHCH2CH2NH2.2HC1 (FW 259.18)
Deionized Water
Dissolve 1 g of NED in approximately 900mL of deionized water contained in a 1L volumetric
flask. Dilute the solution to the mark with deionized water. Mix well. Store the solution in an amber
bottle in a refrigerator.
Sampler Wash
Deionized Water
The sampler wash solution should have the same acid content as the samples and calibrants. If
the samples have been preserved with 2ml of concentrated sulfuric acid per liter of sample, use a
solution of the same composition for the sampler wash.
Calibrants
Stock 1000 mg L-1 Nitrate Nitrogen (1L)
Potassium Nitrate, dried at 110 degrees C 7.2187 g
KNO3 (FW 101.11)
Deionized Water
CHCI3 • 2 drops
Dissolve 7.2187 g of dry potassium nitrate in approximately 900mL of deionized water contained in a
1L volumetric flask. Dilute the solution to the mark with deionized water and mix it will. Add 2 drops
of chloroform. Store the stock nitrate calibrant at 2 - 6 degrees C.
Stock 1000 mg L-1 Nitrite Nitrogen (1L)
Sodium Nitrite dried at 110 degrees C 4.9262 g
Deionized Water
CHCI3 2 drops
Dissolve 4.9262 g of solium nitrite in approximately 900mL of deionized water contained in a 1L
volumetric flask. Dilute the solution to the mark with deionized water and mix it well. Add 2 drops of
chloroform. Store the stock nitrite calibrant at 2 - 6 degrees C.
Intermediate Calibrant 100 mg L-1 (100mL)
Stock Calibrant 1000 mg L-1 Nitrogen 10.0mL
Deionized Water
-------
Appendix B
Revision No 6
Date- April 30, 1990
Page 5 of 8
With a volumetric pipet add 10mL of stock caltbrant to approximately 85mL of deionized water
contained in a 100mL volumetric flask. Dilute the solution to the mark with deionized water and mix it
well. Prepare the intermediate calibrant daily.
Working Calibrants (100mL)
Use adjustable, microliter pipettes to add the designated volumes of intermediate or stock
calibrant to the required number of 100mL volumetric flasks that each contain approximately 95mL of
deionized water. Dilute each solution to the mark with deionized water and mix it well. If the samples
are preserved with sulfuric acid, add acid in the same proportion to each volumetric flask. Prepare
working calibrants daily as suggested in the table below.
Nominal Concentration (mg L-1)
0.01
0.02
0.05
0,1
0.5
0.7
1.0
0.1
0.5
1
5
10
50
100
Intermediate Calibrant Volume (uL)
10
20
50
100
500
700
1,000
Stock Calibrant Volume (uL)
10
50
100
500
1,000
5,000
10,000
Open Tubular Cadmium Reactor (OTCR) (4)
The RFA analytical cartridge uses an OTCR rather than a packed bed cadmium reactor (PBCR)
to reduce nitrate to nitrite. Nitrogen is used to segment the analytical stream to prevent a pH increase
due to reaction between oxygen in ambient air and cadmium. The buffer capacity of imidazole is
sufficient to compensate for dissolved oxygen in samples and reagents of the cadmium tube.
Deposits of cadmium hydroxide reduce the reduction capacity of the cadmium.
Reagents for OTCR Activation
Stock Imidazole Buffer, 0.1M
previously prepared
Cupric Sulfate, 2% w/v (1L)
-------
Appendix B
Revision No 6
Date. April 30, 1990
Page 6 of 8
Cupric Sulfate 20 g
CuS04.5H20 (FW 249.69)
Deionized Water
Dissolve 20 g of cupric sulfate in approximately 900mL of deionized water contained in a 1L
volumetric flask. Dilute the solution to the mark with deionized water and mix it well.
Buffered Copper Solution (40ml_)
Stock Imidazole Buffer 20mL
Cupric Sulfate, 2% w/v 20mL
Mix together 20ml_ of imidazole buffer and 20mL of 2% cupric sulfate in a 50mL beaker.
OTCR Activation
The OTCR (ALPKEM part number A303-0500-12) is a coiled cadmium tube (12") that has been
cleaned of manufacturing oils inside and coated with a clear acrylic polymer. Short lengths of
0.034"ID polyethylene are sleeved to the reactor coil. The free ends of polyethylene are sleeved to
allow installation of the reactor in the manifold. These sleeves are joined by a short length of heavy
walled polyethylene tubing.
Procedure
1. Detach one sleeve from the heavy walled polyethylene tubing. Attach a syringe
(lOcc) to the tubing with a short length of 0.100"ID pvc.
2. Place the free sleeved end of the reactor into the beaker of buffered copper solution
and draw approximately 5mL of the solution through the OTCR. Wait for 2 minutes
with the buffered copper solution filling the reactor.
3. Repeat step 2 twice more.
4. Place approximately 20ml_ of stock imidazole buffer into a 50mL beaker. Draw the
buffer through the OTCR flushing through any bits of debris from the copperization
process. Leave the reactor filled with buffer and reattach the sleeved ends with the
heavy walled polyethylene.
NOTE: Do not introduce air into the cadmium tube during this process.
5. Before each day's run, reactivate the OTCR by filling the reactor with buffered
copper solution as in step 2 once only and flushing it with stock imidazole buffer
(step 4).
Installation of the OTCR
The analytical cartridge is provided with a jumper of 0.034"ID polyethylene sleeved at both ends
in the position where the OTCR is to be installed.
-------
Appendix 8
Revision No 6
Date: April 30, 1990
Page 7 of 8
1. With the jumper in place, pump reagents segmented with nitrogen until a stable flow
is established.
NOTE: The working buffer must be in the cartridge before the OTCR is installed.
2. Turn the pump off and remove the polyethylene jumper.
3. Install the OTCR in place of the jumper removing the piece of heavy walled
polyethylene tubing.
4. Resume pumping and wait until a stable bubble pattern is established before
proceeding with the determinations.
Removal of the OTCR
1. Before the reagent lines are removed from the reagents, stop the pump, remove the
OTCR and install the jumper.
2. Resume pumping, place the reagent lines in distilled water and pump until the
cartridge has been thoroughly cleaned of reagents.
3. Place the piece of heavy walled polyethylene in one of the sleeved ends attached to
the OTCR. Attach the syringe with 0.100"ID tubing to the heavy walled polyethylene.
Draw 10 to 15mL of stock imidazole buffer through the reactor. Leaving buffer in
the cadmium tubing, remove the syringe and join the sleeved ends with the heavy
walled polyethylene tubing.
NOTE: Do not leave any air in the OTCR. It must be stored filled with stock
imidazole buffer.
Reduction Efficiency and Stabilization of the OTCR
In the OTCR nitrate is reduced to nitrite. However, under some conditions reduction may
proceed further with nitrite being reduced to hydroxylamine and ammonia. These reactions are pH
dependent.
NO3- + 2H+ + 2e- NO2- + H2O (1)
NO2- + 6H+ + 4e- H3NOH+ + H2O (2)
NO2- + 8H+ + 6e- NH4 + + 2H2O (3)
At the buffered pH 7.5 of the reaction, equation 1 predominates. However, if the cadmium surface is
overly active, equation 2 will proceed sufficiently to give low results. If the cadmium surface is
insufficiently active there will be a low recovery of nitrate as nitrite (5). This latter is defined as poor
reduction efficiency.
To determine the reduction efficiency, run a high level nitrite calibrant followed by a nitrate
calibrant of the same nominal concentration. The reduction efficiency is calculated as follows:
(N02-"peak height) - (NO3- peak height) x 100 = % reduction efficiency NO2- peak height
If the response of the nitrite is as expected but the reactor efficiency is poor it may be necessary to
repeat the activation procedure. However, if the nitrite response is much less than expected it is an
indication that the nitrite is being further reduced and stabilization of the OTRC is necessary.
-------
Appendix B
Revision No. 6
Date: April 30, 1990
Page 8 of 8
With some types of samples, notably those of high chloride content such as potassium chloride
soil extract or seawater samples, a longer OTCR may be necessary and/or a greater amount of
copper may be added to the working buffer.
Stabilization
When an OTCR is first activated it may be necessary to stabilize the activity of the reactor. In
order to stabilize the OTCR, pump a mid or high calibrant continuously and record the steady state
signal. Continue the steady state until a drift is no longer observed. Return the sampler probe to
wash and proceed with determinations when the baseline has stabilized.
The small amount of copper in the working buffer serves to maintain the reactor in a stable
reactive condition.
References
1. Standard Methods for the Examination of Water and Wastewater, Fourteenth Edition, 1976
American Public Health Association, Washington, D.C., pp. 424-425, 434.
2. F. Nydahl, Talanta 23, 349-357 (1976).
3. Methods for Chemical Analysis of Water and Wastes, March 1984, EPA-600/4-79-020, 'Sample
Preservation", p. xvii, Environmental Monitoring and Support Laboratory, Office of Research and
Development, U.S. Environmental Protection Agency, Cincinnati, OH 45286.
4. Patton, C.J., Doctoral Dissertation, Michigan State University, 1982, pp. 87-121.
5. J.B. Fox, Anal. Chem., 51, 1493 (1979).
6. G. Norwitz and P.N. Keliher, Analyst, 109, 1281 (1984).
TMRFA is a registered trademark of ALPKEM Corporation, Clackamas, Oregon 97015.
RBnj-35 is a registered trademark of ICI Americas, Wilmington, DE.
Copyright 1986, ALPKEM Corporation, Clackamas, OR 97015.
-------
Appendix C
Revision No 6
Date- April 30, 1990
Page 1 of 5
APPENDIX C
FORMAT FOR NPS DATA FILES
-------
Appendix C
Revision No. 6
Date April 30, 1990
Page 2 of 5
APPENDIX C
FORMAT FOR NPS DATA FILES
Format for National Pesticide Survey (NPS) Data
LINE
1
2
COLUMNS
1-6
9-14
17-24
27-34
37-44
47-54
57-64
68-69
1-6
9-14
17-24
27-34
37-44
47-54
57-64
68-69
DESCRIPTION
Fid pH
S_Temp
Date_Sam
Date_Shp
Date_Rec
Time_Sam
Timejce
pH Note: Method 9 only
enter pH OF FIELD SAMPLE
enter STABILIZED TEMPERATURE OF WATER
enter DATE SAMPLED
enter DATE SHIPPED
enter DATE RECEIVED
enter TIME SAMPLED
Enter TIME ICED
enter pH Note: Method 9 only
3
4
5
6
7
BLANK
1-17
1-80
BLANK
1-6
16-18
21-25
28-35
38-45
48-55
58-63
1-14
16-18
21-25
28-35
38-45
48-55
58-63
Receipt Condition
enter CONDITION OF SAMPLE UPON RECEIPT AT
LABORATORY
Samp #
Lab
Set #
Date_Spk
Date_Ext
Date_Ana
Column
enter SAMPLE IDENTIFICATION NUMBER
enter LAB ABBREVIATION (JMM)
enter SET NUMBER
enter DATE SPIKED
enter DATE EXTRACTED
enter DATE ANALYZED
enter ANALYSIS COLUMN
BLANK
-------
Appendix C
Revision No 6
Date. April 30, 1990
Page 3 of 5
LINE
10
11
12
13
14
15
16
17-??
COLUMNS
1-4
8-13
16-22
25-31
34-40
43-49
52-60
65-70
1-5
8-13
16-22
25-31
34-40
43-49
52-62
65-70
BLANK
1-8
1-80
BLANK
1-7
29-33
39-45
67-71
1-25
28-34
39-63
66-72
DESCRIPTION
Type
Spiker
Extract
Analyst
Sam Vol
Ext_Vol
Int. Std.
% Surr
enter SAMPLE TYPE
enter SPIKER'S INITIALS
enter EXTRACTOR'S INITIALS
enter ANALYST'S INITIALS
enter VOLUME OF SAMPLE
enter VOLUME OF EXTRACT
enter PERCENT RECOVERY OF INTERNAL STANDARD AS
COMPARED AGAINST THE CALIBRATION STANDARD
enter PERCENT RECOVERY OF SURROGATE
Comments
enter ANY PERTINENT COMMENTS ON SAMPLE AND
ANALYSIS
Analyte
Cone.
Analyte
Cone.
enter ANALYTE'S NAME
enter CONCENTRATION OR PERCENT RECOVERY
enter ANALYTE'S NAME
enter CONCENTRATION OR PERCENT RECOVERY
-------
Appendix C
Revision No 6
Date April 30, 1990
Page 4 of 5
LINE
1
2
3-?9
1)
2)
3)
4)
FORMAT FOR NFS INSTRUMENT CONTROL DATA
COLUMNS DESCRIPTION
1-3
6-11
14-21
24-30
35-37
42-44
49-51
55-58
BLANK
1-3
6-11
14-21
24-30
33-37
40-44
47-51
54-58
Lab
Method
Date_Ana
Analyst
S/N
PSF
PGF
Res.
enter LAB ABBREVIATION (JMM)
enter METHOD NUMBER
enter DATE ANALYZED
enter ANALYST'S INITIALS
enter SIGNAL TO NOISE RATIO
enter PEAK SYMMETRY FACTOR
enter PEAK GEOMETRY FACTOR
enter RESOLUTION
NOTES ON NFS FORMAT
The format for any date is mm/dd/yy. A missing date should be entered as 01/01/60.
The format for any time is hh:mm is 24 hour format. A missing time should be 00:00.
Any other data that is missing
The number of decimal places
Concentration
Percent Recovery
Internal Standard
should be entered with a period (.).
should be as follows:
3 (significant figures)
1
1 (percent recovery)
Instrument Controls 2
5)
PH
Temperature
Volumes
1 (method 9 only)
0
0
The code for columns is as follows:
Primary
Confirmatory
Third
PRIM
CONF
GCMS
6) The laboratory code for Montgomery is JMM
-------
Appendix C
Revision No 6
Date April 30, 1990
Page 5 of 5
7) The codes for Type are as follows:
Field sample SAMP
Shipping blank SBLK
Method blank MBLK
Lab control standard LCS@
Lab spike sample LSS@#
Time storage extract day 14 HTE@
Time storage sample day 14 HTS@
Time storage sample day 0 DTS@
where @ is the mix letter (A, B, C) and # is the spiking level (0, 1, 2,or 3)
8) There should be at least one blank line between samples in the NFS data file.
9) The codes for Concentration and Percent Recoveries are as follows:
Not Analyzed . (period)
Not Detected (< 1/2 MRL) -999
Saturated -777
Compound failed LCS but positive by GCMS -666
Compound failed LCS but negative -444
Compound failed LCS but positive, no confirmation needed (spiked) -333
> 1/2 MRL but < MRL, not conf -222
> 1/2 MRL but < MRL, conf not needed -222
> 1/2 MRL but < MRL, conf by GCMS -111
Above MRL but not quantified (as for GCMS or qualitative cmpds) 888
10) If a reported value is greater the (>) some number in the NPS instrument control data, then
use a minus sign (-) instead of >.
-------
Appendix D
Revision No 6
Date- April 30, 1990
Page 1 of 5
APPENDIX D
DIXON'S TEST
-------
DIXON'S TEST
Dixon's test is used to confirm the suspicion of outliers of a set of data
(for example, control chart data points). It is based on ranking the data
points and testing the extreme values for credibility. Dixon's test is based
on the ratios of differences between observations and does not involve the
calculation of standard deviations.
The procedure for Dixon's test is as follows (from Taylor, 1987):
1) The data is ranked in order of increasing numerical value. For
example :
2) Decide whether the smallest, X^ or the largest, XTl, is
suspected to be an outlier.
3) Select the risk you are willing to take for false rejection.
For use in this QAPP we will be using a 5% risk of false
rejection.
4) Compute one of the ratios in Table 1. For use in this QAPP we
will be using ratio i22, since we will be using between 20 and
17 points for the control charts.
5) Compare the ratio calculated in Step 4 with the appropriate
values in Table 2. If the calculated ratio is greater than the
tabulated value, rejection may be made with the tbulated risk.
Fort his QAPP we will be using the 5% risk values (bolded) .
Example (from Taylor)
Given the following set of ranked data:
10.45, 10.47, 10.47, 10.48, 10.49, 10.50, 10.50, 10.53, 10.58
The value 10.58 is suspected of being an outlier.
1) Calculate ru
10.58 - 10.53 0.05
ru - ............. - ---- - 0.454
10.58 - 10.47 0.11
2) A 5% risk of false rejection (Table 2), rn - 0.477
3) Therefore there is no reason to reject the value 10.58.
4) Note that at a 10X risk of false rejection ru - 0.409, and the value
10.58 would be rejected.
-------
TABLE 1
CALCULATION OF RATIOS
For use if if X,, is
Ratio n is between suspect
(Xn ' Vl>
j. 3-7
r10 o /
fv Y '»
(,An - AI;
fv Y ^
(•Xn -^n-l)
r,, 8-10
f Y Y ^
\ *T1 " A2 /
(Xn - V2)
r., 11-13
j-2i J.J. J.J
/Y Y ^
^•'hj " A2/
r_n 14 - ?S
i. 22 j.4. ^3
(Xn - Xj)
if Xj is
suspect
(X2 - Xx)
-------
Ratio
-10
•ii
L21
TABLE 2
VALUES FOR USE WITH THE DIXON TEST FOR OUTLIERS
0.5%
Risk of False Rejection
11 1%
10%
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
0.994
0.926
0.821
0.740
0.080
0.725
0.677
0.639
0.713
0.675
0.649
0.674
0.647
0.624
0.605
0.589
0.575
0.562
0.988
0.889
0.780
0.698
0.637
0.683
0.635
0.597
0.679
0.642
0.615
0.641
0.616
0.595
0.577
0.561
0.547
0.535
0.524
0.514
0.505
0.497
0.489
0.941
0.765
0.642
0.560
0.507
0.554
0.512
0.477
0.576
0.546
0.521
0.546
0.525
0.507
0.490
0.475
0.462
0.450
0.440
0.430
0.421
0.413
0.406
0.806
0.679
0.557
0.482
0.434
0.479
0.441
0.409
0.517
0.490
0.467
0.492
0.472
0.454
0.438
0.424
0.412
0.401
0.391
0.382
0.374
0.367
0.360
Note that for this QAPjP the 5% risk level will be used for ratio r22.
-------
Reference:
John K. Taylor, Quality Assurance of Chemir.al Measurp.iTu.rn-c Lewis
Publishers, Chelsea, MI, 1987.
-------
Appendix E
Revision No. 6
Date- April 30, 1990
Page 1 of 3
APPENDIX E
ROUNDING AND SIGNIFICANT FIGURES
-------
Chapwr 7
DATA HANDLING AND REPORTING
7.1 Introduction
To obtain meaningful data on water quality, the sample coilector must obtain a
representative sample and then deliver it unchanged for analysis. The analyst must perform
the proper analysis in the prescnbed fashion, complete calculations, and convert results to
final form for permanent recording of the analytical data in mearungful, exact terms. These
results are transferred to a storage facility for future interpretation and use.
The following sections discuss processing of actual values, recording and reporting of data in
the proper way, some means of quality control of data, and the storage and retrieval of data.
7.2 Tht Analytical Valui
7.2.1 Significant Figura
The term "significant figure" is used, sometimes rather loosely, to describe a judgment of
the reportable digits in a result. When the judgment is not soundly based, mearungful digits
are lost or meaningless digits are reported. On the other hand, proper use of significant
figures gives an indication of the reliability of the analytical method used.
The following discussion describes the process of retention of significant figures.
A number is an expression of quantity. A figure or digit is any of the characters 0, 1, 2, 3, 4,
5, 6, 7, 8, 9, which, alone or in combination, serve to express a number. A significant figure
is a digit that denotes the amount of the quantity in the particular decimal place in which it
stands. Reported analytical values should contain only significant figures. A value is made
up of significant figures when it contains ail digits known to be true and one last digit m
doubt. For example, if a value is reported as 18.8 mg/1, the 18 must be firm while the 0.8 is
somewhat uncertain, but presumably better than one of the values 0.7 or 0.9 would be.
The number zero may or may not be a significant figure depending on the situation.
Final zeros after a decimal point are always meant to be significant figures. For example, to
the nearest milligram. 9.8 g is reported as 9 800 g.
Zeros before a decimal point with nonzero digits preceding them are significant. With no
preceding nonzero digit, a zero before the decimal point is not significant.
If there are no nonzero digits preceding a decimal point, the zeros after the decimal point
but preceding other nonzero digits are not significant. These zeros only indicate the position
of the decimal point.
Final zeros in a whole number may or may not be significant. In a conductivity
measurement of 1,000 ^mho/cm, there is no implication by convention that the conductiv-
ity is 1.000 t 1 Mm ho. Rather, the zeros only indicate the magnitude of the number.
7-1
-------
When one number is subtracted from another, rounding off should be completed after the
subtraction operation, to avoid possible invalidation of the operation.
When two numbers are to be multiplied, all digits are earned through the operation, then
the product is rounded off to the number of significant digits of the multiplier with the
fewer significant digits.
When two numbers are to be divided, the division is earned out on the two numbers using
all digits. Then the quotient is rounded off to the number of significant digits of the divisor
or dividend, whichever has the fewer.
When a number contains n significant digits, its root can be relied on for n digits, but its
power can rarely be relied on for n digits.
7.2.2.3 Rounding Off the Results of a Siriis of Arithmetic Operations
The preceding rules for rounding off are reasonable for most caJculations; however, when
dealing with two nearly equal numbers, there is a danger of loss of all significance when
applied to a senes of computations that rely on a relatively small difference in two values.
Examples are calculation of variance and standard deviation. The recommended procedure is
to carry several extra figures through the calculations and then to round off the final answer
to the proper number of significant figures.
7.3 Glossary of Statistical Ttrms
To clarify the meanings of statistical reports and evaluations of water quality data, the
following statistical terms are introduced. They are derived in part from usage (1,2) of the
American Society for Quality Control.
Accuracy -The difference between an average value and the true value when the latter is
known or assumed.
Arithmetic mean -The arithmetic mean (or average) of a set of n values is the sum of the
values divided by n:
Bias -A systematic error due to the experimental method that causes the measured values to
deviate from the true vaJue.
Confidence limit. 95 per cent -The limits of the range of analytical values within which a
single analysis will be included 95 percent of the time,
95percentCL = f t \.96S
where CL is the confidence level and S is the estimate of the standard deviation.
7-3
-------
Appendix F
Revision No 6
Date- April 30, 1990
Page 1 of 17
APPENDIX F
NPSIS SAMPLE RECEIPT SOFTWARE FOR LABORATORIES
-------
V5/8I
TO: AKDREV EASTOR, JAMES M. MORTGGMERT CCHSULXARTS
FROM: CHIP LESTER, ICT INC.
RE: HPSIS SAMPLE RECEIPT SOFTIARE FOB. LABORATORIES
ICF's National Pesticide Survey Infonnacion System (NPSIS) is ready to
coLlecc information from you regarding the receipt of well water samples and
their condition. Please find enclosed the following items: 1) A users memo
containing all operating instructions, and 2) A copy of Carbon Copy software
which is necessary to establish communications with NPSIS over phone lines.
As mentioned previously, the software allows you to report the receipt of a
one or more sample kits. It also prompts you for details regarding the
condition of the samples. Additional features include; a bulletin board whic
allows you to interactively send messages to ICF staff via your computer
keyboard, file transfer, and access to the ICF computerized mail system for
sending memos. It is also possible for you to speak over the phon* to an ICF
staff member during your session.
It is important that you test the communications link between the NPSIS
computer and yours. Ve have experienced trouble when using Carbon Copy
software with a computer which has a Manzana 3.5 inch disk drive, and also
with computers which have a non-Hercules or non-EGA compatible graphics card.
For testing purposes, your sample kit identification numbers and FedEx
airbill numbers (respectively) are PD-0000-151 and 1111111111, PD-0000-152
and 2222222222, and PD-0000-153 and 3333333333. Use these sample kit
identification numbers when cryvr.g ouc the N'PSIS Sample Receipts Program.
:r ::-•;:• these will be -:::?---- f:r -each lab
Ve feel that it would be nei.pf.iL co both parties if you could call us
when you are ready to test the '.?SI5 svstem. and we vill assist you over the
phone during your session. If vou jould Like to do this, please call Been
Estrada ac (703) 934-3431. NPSIS will be available for access 24-hours a day.
seven days a week. Ve appreciate hearing any comments you have regarding
NPSIS.
-------
THE KPSIS SAMPLE RECEIPT PROGRAM
NPSIS is designed Co keep crack of che day co day operations of che
National Pescicide Survey. You play an important role in NPS and your ciaely
notification of receiving a kic of samples is essencial Co che success of NFS.
We have designed che Sample Receipt Program with your busy schedule in aind.
SPSIS will obtain che aininum amount of information necessary while scill
maintaining a secure syscea. You will be entering daca inco che NPS IS
personal computer via your own coaputer, taodam, and Carbon Copy sofcvare.
1.1 Hardware and Software Requirements
The NPSIS Sample Receipt Program has a minimum hardware and software
requirement. Here is a list of items you will need:
Hardware:
One (1) IBM PC, XT, AT, or Personal System model with at
least 640K memory.
On* (1) 2400 or 1200 baud Hayes or Hayes compatible modea
with cables. (See Carbon Copy guide for cabling requir-
ements and a description of usable modems)
On* (1) data transmission phone line.
Sofcvare:
• NPSIS Sample Receipt Program access provided for you by
• One (1) copy Carbon Copy sofcvare which is provided co
by ICF for che duration of NPS.
1.2 Initial Installation Steos.
before you can access and use NPSIS. you oust first load the Carbon Copy
software onto your PC. The directions are provided in the Carbon Copy manual.
On* item you will want to include is an entry inco th* "Call Table'. This
entry will include a name, telephone number, and password for th* NPSIS
computer. To enter these items into the Call Table, press "2" from the Carbon
Copy Parameters' Screen. Th* information you must enter consists of th*
following:
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Name: NFS
Telephone Number: 703-961-0629
Password: NPS
NPSIS will maintain a sec configuration throughout operation-. Any
changes due to updates in equipment or the ays tea which will affect your
ability to communicate through Carbon Copy will be forwarded to you. The
paraaeters which will be maintained at this time are:
• 2400 baud modem speed.
• Answer ring count equal Co one.
• Re-booc on exit after 5 minutes. (If there Is a power
failure or some ocher cype of interruption, you can log
back on to NPSIS and resume your session.)
• Five minute inactivity time constraint.
• Two password attempts.
2.1 Establishinz a Communications Lir.k
Once you have installed Carror. ~.3~-: s-a have all of the necessary
Type: C:> CCHELP HPS .- - .: v. rectory containing Carbon Copy
This command will automatically -..». -. ."ilS computer, send your password
for verification, and establish a ^i:a ..-.< secveen the two computers. You
will be able to discern what is :a*.-g pi act by messages to your screen.
2.2 Entering fa Sfjplt Receipt !r:o NPSIS
Once you have established a :<»•* l.r.k ( e.g., are 'logged on'), you will
see on the screen exactly what is -r. :.-.t screen of the NPSIS computer. This
screen you are viewing is the main eenu for the Sample Receipt Program.
Remember that you are controlling :-e NPSIS computer via a 2400 baud phone
line and your typing will appear on :r.e screen at a much slower rate than you
are accustomed to. A few tips on how to use the system are outlined in the
next section.
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2.1 Useful Tins on How co Use
Before you scare, a few things co remember arc:
• Pressing che "Esc" key will cancel all changes for the screen you
are currently in and return you co che previous screen. Pressing
"Esc" ac che Searching Screen returns you co the main menu.
• Pressing "PgDn" or "PgUp* will save che items you have entered in
che current screen and place you in che next or previous screen,
respectively. This feature is handy to use when you only have a fev
items to enter in a screen which prompts for several items.
• Pressing "Enter", "arrow up", or "arrow down* will move the cursor
from field co field in each screen. Remember chat using the
sideways arrows will noc work.
• Pressing che "Ale" and "Right Shift* keys together will place the
Carbon Copy Control Screen over che NPSIS Sample Receipt Program.
You can Chen use che comaunicacions features in Carbon Copy.
Pressing "F10" again when you are through will replace the NPSIS
Sample Receipt Program screen you were currently in back on your
screen, and
• Because you will are most Likely co be entering information
regarding a number of kits at one time, after you save or cancel
your entries for one kit, you will be placed ac the initial Sample
Searching Screen for a new kit. If you are finished with your data
entry, simply press "Esc* co exit the Sample Searching screen and be
placed in the main menu.
2.3 A Basic O'-Cline of che Sample P.ece'.s: °7°g7a'iPi
The NPSIS Saaple Receipt Prozraa r.as three basic feacures :
• Initial repor :..-£ :: - ...-a staple kit of saapie borz.es
• Ability co ec.: :: :i *ci: an existing report of a ici:
receipt, anc
• Access to ICFs computerized mail system which provides che
ability to se-d a«aoranda co ICF staff.
The Information obtained ir. jr «ncry for a kic of boccles is:
• The kit idencif -.cation number, Che FedEx airbill number,
and che last naste of the person making the entry.
• Any damage to :.".• kit as a whole such as melted ice or any
breakage of the cooler
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• Verification of which bottles belong in a kit or cooler
notification of *ny Hissing beetles or any additional
bottles, and
• Any damage to each sample bottle which renders it unusafc
for analysis and testing.
NPSIS ^fTfle Receipt °rngrj"fl Screens.
When you have completed the logon procedure, you will see th« following
main menu on your computer screen:
NATIONAL PESTICIDE SURVEY INFORMATION SYSTEM
SELECTION MENU FOR REPORTING SAMPLE RECEIPTS 04/05/88
Report \ Edit a Sample Receipt
Send a Memo
Press to Logoff
use f ^and ^ ~o selec: option.
The screens provided in this memo will show all of the screens available
and thus represent the maximum number of screens you will encounter with
NPSIS. It is most likely chat you will not have the need to enter information
reporting diaaged kits or samples. Therefore, not all of the screens depicted
below will appear in your normal session.
If you choose the first item on the menu. 'Report \ Edit * Sanple
Receipt", you will then be prompted for the kit identification number and the
FedEx airbill number associated with the specified kit. The screen will
appear like this:
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NPS SAmple Receipt Searching Screen
** Enter che following items to access kit information **
To find the Kit information in NPSIS in the most coaplete
and accurate fashion, please enter the Kit number and che
FedEx airbill number.
Enter kit number:
> PD-0001-151
Enter FedEx airbill *:
> 1111111111
Enter your last name:
> CHIAMG
* Press ESC to exit che searching *
If the kic number you have entered is incorrect, or if the kit number and
FedEx airbill number combination is incorrect, NPSIS will prompt you to try to
enter these number again, as illustrated on the next page. It is possible
chat the FedEx airbill number on the kit is not the same as the FedEx airbill
number which was entered into the NPSIS system. This could happen if the
field team loses or damages the airbill.
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ERROR!! The kic you entered cannot be found. .
Kic nunber: PD-0001-151
AND
FedEx airbill nunber: 1111111111
Please check these numbers «nd try Again 1
******* ********** ****•*****•*•*•****
****************************
NPSIS is designed to crack Kits and FedEx airbill numbers.
The Kit and FedEx airbill number combination you have entered
does not match what is currently in the system. Please enter
che correct combinacion. If you scill have problems, cry
Leaving che FedEx airbill * BLANK. Only enter che Kic number.
*-*•*•* ********"*•*** •* *•*••*•'* ****** It-*-***-*-*-*"*"*- ***************************
Press any key to continue...
Then, you will encounter this screen insuring chat you have entered che
FedEx airbill number:
Kit No.: PD-0001-151
Did vou enter Che correct Kic number and FedEx airbill number"
NrsIS is designed Co score ana rractc a*. .rea£x airaiii r.umoers.
This Kit may have a differenc FedEx airbill number Chan che
system, please enter che new FedEx airbill number'
Note: if the correct airbill number was entered before, hit ENTER.
PgDn (Next p«g«). PgUp (Previous page), Esc (Exit)
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One* you have correccly identified the staple kit, NPSIS will ask you if
chera is any damage co cha kic as a whole:
Kic No.: PD-0001-151
Was there any daaage co che saople kic? (Y/N)
PgDn (Next pmge), PgUp (Previous page), Esc (Exit)
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If you press «Y', NPSIS will then pronpc you for the apparent cau*e of
damage:
Kit No.: PD-OOOl-151
Was there any damage co the sample kic? (Y/N)
Please indicate the cause for damage:
Kit is broken (Y/N) T
Ice is aelted (Y/N)
Other Reason (Y/N)
Please enter any comments about the sample kit.
Comments: Broken upon arrival.
Comments:
PgDn (Next page), PgUp (Previous page), us* 4 I or <*-J to select field.
There may already be comments regarding the kit in the comment field
shown in the above screen. In this case, please enter your comments after any
which already appear. This insures that no information is destroyed.
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Next. NPSIS will ask vou to survey the contents of the kit and check ch*t
which bottle* «re contained wichin che kit. You should then look at the
bottle label* and determine if any are missing. Don't forget to check and
determine if any bottles have been included in the kit which do not aooear on
che list provided by NPSIS on this screen:
Kit No.: PD-0001-151
Ple**e compare the following bottle numbers
with those in the sample kit.
Bottle No: PD-0001-l-i-01
Bottle No: PD-0001-1-1-03
Bottle No: PD-0001-1-3-01
Bottle No: PD-0001-1-3-03
Bottle No: PD-0001-1-9-01
Bottle No: PD-0001-1-9-03
Did you receive exactly these bottles in the sample kit? (Y/N)
PgDn (Next page), PgUp (Previous page), Esc (Exit)
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If you hav« pressed "N", indicating that you did not receive exactly what
MPSIS assuaes you have received, you will be prompted to enter the appropriate
information. This inforaation includes pressing « "Y" or * *N" beside each
boccle, and entering che bottle number found on the labels of any Additional
bottles you have received:
Kit
1.
3.
5.
7.
So.: PD-0001-151
Please indicate which
Bottle No:
PD-0001-1-1-01
PD-0001-1-1-03
PD-0001-1-3-01
PD-0001-1-3-03
PD- 0001-1-9-01
PD-0001-1-9-03
Please indicate any
Bottle No. PD-0002-1-
Bottle No. PD-0004-4-
Bottle No.
Bottle No. - - -
bottles you received:
Received (Y/N)
R
H
T
Y
Y
Y
additional bottles you received:
1-05 2. Bottle No. PD-OO02- 2-2-01
4-01 4. Bottle No. - - - -
6. Bottle No. - ...
8. Bottle No. • ...
PgDn (Next page), PgUp (Previous page), use f |or •«—'to select field.
Notice chat the user has indicated chat he did not receive the first two
bottles on the list. Also note chac the user has indicated additional bottles
vhich have come in the saarole kic. but whicn were not on the list.
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Nexc, NFSIS prompts you co indicate if any of the individual bottles have
been daaaged and rendered unusable for analysis:
KiC No.: PD-0001-151
Vas there any daoag* co ch« sample Bottle*? (Y/N) T
PgDn (Next page), PgUp (Previous page), Esc (Exit)
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In order to complete the appropriate information on damaged sasml*. v«,,
•use first pr..« « «Y' or a 'N- In the field labeled 'Damaged Y/N- if vJ!
have entered a -Y- In this fl.ld, you oust then ld«nttfy vtuc th« cau.. a? th.
doug* is. to th« b.sc of your abtliti.s. AJ noctd on th« conpuc.r ser.In
b.low. ch« "Oth«r« c.t.gory should b« u*«d if th« supl« ij unusmbl. bue i«
noc brok«n. ?!•*>• cry to cona«nt wh«n«v«r possibl*.
Kit Ho.: PD-0001-151
?!•«»• indic*t« which beetlas «r« cUaag.d by «nt«ring Y or H
«nd for tho«« which are daaaged, indlc*c« th« c«u«« of
---CAUSE---
Bottle No: Damaged Broken Other Comment
(Y/N) (Y/N) (Y/N)
PD-0001-1-3-01 H
PD-0001-1-3-03 •
PD-0001-1-9-01 H
PD-0001-1-9-03 B
PD-0002-1-1-05 §
PD-0002-2-2-01 T Y
PD-0004-4-4-01 •
The 'Other' cause category is for reporting contamination of a saople,
e.g. contaaination noted on the Sample Tracking Form, air bubbles,
or other reasons a sample is unusable.
PgDn (Next page), PgUp (Previous page), use
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Mow you have completed all of che necessary information needed to verify
chat the proper samples have reached their final destination in usable
condition. You may save your kit entry by pressing "Enter". If you wish to
cancel your kit entry and try again, press "ft" and 'Enter'. If you wish to
view or edit the current kit entry, press "R" and "Enter" and NPSIS will place
you back at the beginning of your entry.
You have coapleted all of the data entry screens for this Kit.
You may save your entry by pressing 'Enter'.
You may cancel your entry by pressing 'N' and 'Enter'.
You may verify or edit chis entry by pressing 'R' and 'Enter'.
* * * Accept entries? * * *
co Save *
Co Cancel *
co Verify or Edit * T
* Press
* Press N and
* Press R and
By pressing "Enter" , you have saved ail of che information necessary for
a particular sample kit. NPSIS assuaes :!-.a: you will enter acre chan one kit
s-rry rer session. Therefore •-_ - . ''. -- -'. -..*-L a: -re •_-.iT•_s"_ ' :•? = r-.r.l- -.
Screen'. If you are finishea, press £sc i.-.a you will be returned co cr.e
main menu. You can then log off of SPSIS by pressing "Alt" and "Right shifc"
ac che same cime. You may also sena i aeso rr-.rough che ICF computerized mail
system. To do this, cursor down co :.w.e second menu choice and press "Enter".
The next tvo pages of this nemo describe how to use the ICF electronic
mail systea. Note that the password for you is NFS. The nail system software
program will proeq>t you for this password before Ic will allow access to the
system. Also, when you are selecting che recipients of your memo, please
press che space bar beside the inicials *WW This will send your BMSM> to
•11 1C? staff involved in the NFS project If you wish to send OMSJOS to a
particular ICT staff member, please call Beth Estrada for the identification
number of the desired ICF employee.
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ELECTRONIC MAIL
Functioa
Augment office communications
electronic transfer of notes and files.
with
Summary
Electronic Mail (E-Mail) allows you to send,
receive, read, and subsequently save or
discard notes and attached files.
When you power up your workstation you
will automatically enter E-Mail if you have
received any mail. Enter your password to
check your mail, or press twice to
avoid E-Mail and continue to the Assist
main menu.
Instructions
Operation of E-Mail is similar to Lotus
1*2-3. Press the Fl key to receive help at
aay time during operation. If any more
help is needed contact workstation support
to receive a manual.
For more information on any feature of
electronic mail, use Network Courier's on-
line help or refer to the User's Manual.
Passwords
Your password will be 'password' until you
change it yourself. Once you have given
your password and entered E-Mail, you can
change your password by selecting Options,
then Password.
Reading Mail
1. Select 'Read' from your menu.
Highlight read,then press
.
2. Select the note to read:
a. Highlight the note (using
the arrow keys); and press
.
B. To save the note, select
"Storage*, then 'Save*. Enter
the name of the file to which
the note should be saved.
3. Press to select another note.
Writing Mail
1. Select 'Compose', then "edit*.
2. Press when the highlight
moves to TO*.
3. Select the recipients(s):
a. Move the highlight to the
first recipient's initials.
b. Press the space bar. A
small mark will appear.
c. Repeat steps a and b for all
recipients. Press the space bar
twice to 'de-select* recipients.
The small mark will disappear
d. Press <£SC> tc cancci ">?
entire list.
4. Select the initials of those who will
receive copies:
a. Press the down arrow to move
to 'CC.
b. Select recipients as instructed
above (step 3, a-d)
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Writiac Mail, coitimtd
5. Eater a subject and priority.
(optional)
6. Select attachments (optional):
a. Press and type the
path for the documeat(s).
b. Press and select the
documeat(j) to be attached.
c. Repeat steps a and b for
documents in another directory.
7. Enter the text of your message.
S. Press when finished.
9. Select Transmit* to post the note
and attachments.
Quitting the Mail Program
1. Press from the menu.
2. Select 'YES'.
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Appendix G
Revision No 6
Date. April 30. 1990
Page 1 of 4
APPENDIX G
DATA ARCHIVING SOP
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MONTGOMERY LABORATORIES STANDARD OPERATING
PROCEDURE FOR THE ARCHIVAL OF THE
NATIONAL PESTICIDE SURVEY (NPS) DATA
Introduction
A Standard Operating Procedure has been developed to allow
Montgomery Laboratories (ML) to retrieve all documentation
necessary to technically defend NPS analytical results. The
documents will be located on the first floor on ML premises in a
locked data storage room.
All data that have been collected in support of the National
Pesticide Survey will be stored until October of 1992 in a
systematic manner such that data may be retrieved in a timely
fashion for reference purposes.
The NPS project manager, Julie Zalikowski, will be the primary
manager for all archived documents. Ms. Zalikowski and Dr. Eaton,
the program manager, will maintain keys to the storage room.
Materials to Archive
1) Method 1 Initial demonstration of capabilities.
2) Since samples are filed by sets, a cross-reference list from
sample ID to set ID has been developed. The cross-reference
list includes:
Sample ID
Sample type
Date sampled
Date received
Date extracted
Set numbers
Date analyzed
3) Method 1 chromatograms listed in chronological order
1 - 0001 through 1 - 0196
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4) Method 1 Quantitation reports listed in numerical order.
1 - 0001 through 1 - 0196
For each Quantitation report the following materials are
available, as appropriate to a given method and /or set:
Set completion form
Method Blank (MBLK)
Corrective Action Forms
Lab control standards (LCS's)
Lab spike samples (LSS's)
Instrument control samples (ICS's)
Field samples
Time - storage samples
Control chart
GC/MS data (Extract shipping forms and spectras)
Extraction summary sheet
Sample tracking
Obase hard copy
Analytical run sheet
5) Method 1 control charts
1 - 1 through 1 - 37
6) Method 3 Initial demonstration of capabilities
7) Method 3 Sample ID to set ID cross-reference list
8) Method 3 chromatograms
3 - 0002 through 3-0198
9) Method 3 Quantitation reports
3 - 0002 through 3 - 0198
10) Method 3 Control Charts
3 - 1 through 3 - 39
11) Method 9 Initial demonstration of capabilities
12) Method 9 sample ID to set ID cross-reference list
13) Method 9 Quantitation reports
9 - 01 through 9 - 36
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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14) )CF sample receipt forms
15) Monthly status reports/Internal QA audit reports
16) Statement of qualification for personnel who participated in the
project
1 7) Log books
a. Extractions log book
b. Standards log book (Method 1 & Method 3)
Spiking Standards log
Internal Standards log
Surrogate log
Calibration standards log
c. Method 9 log book
Daily log
Standard & Reagent log book
d. Instrument Maintenance log book
e. GCMS log book
f. Telephone log book and notes (M1, M3 & M9)
18) Forms and records
A Copy of the QAPjP M1, M3, M9
Temperature log
GCMS Extract shipping form
GCMS Reports
Copy of NFS formatted disc
Hardcopy of any specialized computer programs
Time storage extraction and analysis summary
19) Correspondence received from Technical Monitor
20) Performance evaluation results
21) NFS Contract
22) ICF Daily Sampling Schedules
23) General NFS Information
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