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Summary Report of NOAA-NBS

Quality Assurance Workshop

December 1986 , 1988

John K. Taylor, Editor

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Measurement Laboratory

Center for Analytical Chemistry

Gaithersburg, MD 20899

August 1986

U.S DEPARTMENT OF COMMERCE

>r 1REAU OF STANDARDS

-QC

100

.1156

#86-3446

1986

NBSIR 86-3446 Research Information Center

National liureau of Standards

SUMMARY REPORT OF NOAA-NBS

QUALITY ASSURANCE WORKSHOP

DECEMBER 1985, 1986

Gaithersburg, Maryland 20899

L

John K. Taylor, Editor

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Measurement Laboratory

Center for Analytical Chemistry

Gaithersburg, MD 20899

August 1 986

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS. Ernest Ambler. Director

TABLE OF CONTENTS

Page

Introduction 1

The Role of Specimen Banking in the NCAA Status and Trends

Program, R. Zeisler 2

Trace Analysis and Quality Assurance for Extractable Organics

Chemicals, W.D. MacLeod, Jr. • 4

Intercomparison for Trace Metals in Marine Sediments,

S . Berman 12

A Statistical Review of Inter-Laboracory Comparison Data,

R.G. Paule 13

Organic Methods Workshop Summary, S.A. Wise, M.M. Schantz,

and W . E . May 14

Inorganic Methods Workshop Summary, T.C. Rains 17

Long-Term Goals, i.K. Taylor 19

Reference Materials for Marine Analysis, W.E. May 22

Appendix A - Workshop Agenda 25

Appendix B - NBS Report of Analysis 552-86-009 27

Appendix C - SRM Certificates 35

Appendix D - Workshop Attendees 61

iii
.
Summary Report

Quality Assurance workshop

Co-Sponsored by

NOAA-NBS

National Bureau of Standards

Gaithersburg, MD 20899

December 5-6, 1985

Abstract

This report summarizes the proceedings of a methods development, quality

assurance workshop held at the National Bureau of Standards, December 5-6,

1985, as part of NOAA's continuing effort to improve the quality of marine

monitoring data. The workshop consisted of a series of contributed papers and

group discussions of the results of collaborative measurements of a group of

test samples. Summaries of the papers and the group discussions are included

in this report.

INTRODUCTION

The quality of marine monitoring data is of mutual concern of the Ocean

Assessment Division (OAD) of NOAA and to the laboratories that furnish much of

this on a contract basis. Accordingly, NOAA/OAD has entered into an agreement

with the National Bureau of Standards (NBS) to organize and conduct a series of

method development/quality assurance workshops to be held on a regular basis.

The several purposes of these workshops are: (1) to promote intercomparability

of data from the various methods used by OAD contractors; (2) to identify and

seek solutions to problems with various methods and techniques; (3) to discuss

quality assurance practices, their implementation, and their value; (4) to

review results from past interlaboratory comparison exercises and plan future

ones; and (5) to improve the application of statistics to marine environmental

quality measurements.

This report summarizes the proceedings of the first workshop, held at NBS,

Gaithersburg Maryland during December 5-6, 1985. The Agenda, reproduced in

Appendix A, consisted of contributed papers and two concurrent workshops on Inorganic Methods and Organic Methods, respectively. The latter were devoted

to presentations of the results of collaborative measurements of special test

samples and in-depth discussions by the attendees of their experiences gained

in analyzing them. Such feed-back is considered to be essential for both

improving the quality of test materials and for identifying and solving

measurement problems. The texts of the contributed papers and summaries of the

workshops discussions are contained in the following sections of this report.

Conclusion

The response of the attendees of this first workshop has encouraged

OAD/NOAA to sponsor a second workshop to be held at the Northwest and Alaska

Fisheries Center. Seattle Washington, on December 3-4, 1986. A second series

of test samples will have been prepared, distributed, and analyzed by that

time, and the results subjected to statistical evaluation. The discussion of

these results will be a major part of the 1986 workshop.

1
The Role of Specimen Banking in the NOAA

Status and Trends Program

R. Zeisler

National Bureau of Standards

A list of all presently suspected environmental hazardous substances would

contain thousands of chemicals produced in significant quantities around the

world; and industry is adding new compounds to that list every year. In

addition, naturally occurring toxic elements and compounds would be included

which are reentering the environment via industrial processes at rates much

greater than their natural degradation or removal from the biosphere. To

monitor their ecotoxic behavior and discernible effects would require the

analysis of environmental samples for all the hazardous chemicals and their

metabolites or decomposition products. However, this is all but impossible.

Hence, monitoring programs generally focus on the measurement of specific

chemicals that are recognized as hazardous or that may be of particular

interest to a specific study, thus exploiting only a fraction of the

information content of a particular sample at the time of the investigation.

To complement the necessarily limited real-time monitoring activities, the

concept of environmental specimen banking (ESB) has been recognized as an important part of systematic environmental monitoring (1-3). ESB is providing

comprehensive records of the current state of ecosystems without the need for

immediate analysis and without the danger of consumption of the sample before

the desirable information has been extracted. The banked specimens will allow

retrospective analysis of yet unknown pollutants as well as for the use of new

or improved techniques for the determination of presently undetectable chemicals. Systematic and repetitive analyses over time of comparable ESB samples

will yield information on the present distribution and its trends for selected

key chemicals which can be related to a known baseline, i.e., the banked

specimens

.

Several pilot ESB programs were established approximately a decade ago and

have served as nuclei for the development of appropriate approaches on ESB (4)

In the U.S., the Environmental Protection Agency (EPA) and the National Bureau

of Standards (NBS) have been involved in a pilot study to evaluate the

feasibility of ESB as an important part of environmental monitoring. The core objective of the EPA/NBS Pilot National Environmental Specimen Bank (NESB) was

the development of a comprehensive analytical approach for ESB. This has been

demonstrated in the NESB on one specimen type, namely human livers (5). The

experiences gained, the technologies developed, and the analytical approaches

designed in the NESB will now benefit new programs that are presently added to

the initial effort. Although the inclusion of monitor specimens from the

marine environment was planned in the conception of the NESB, the inclusion or samples from the National Status and Trends (NS&T) Program will be the first

large scale implementation of ESB in the U.S. for the marine environment.

The NS&T Program will be supported through the development of verified

protocols for taking, handling, preparing and storing of various indicator

specimens collected in the estuarine and coastal waters. These protocols ire

2
designed to ensure validity of the banked samples in terms of non-alterea

chemical composition from the time the sample is taken to the time of analysis.

Approximately 20% of the sites will be selected in each year for banking of the

respective specimens, thus providing a complete archive of all sites within

five years. A selected number of key specimens will be analyzed with

methodology developed in the NESB to provide real-time benchmark data for

reference and comparison with other analysts' and analytical methods.

References

1. Berlin, A., Wolff, A.H. ; Hasegawa, Y. , Eds. "The Use of 3iological Specimens

for the Assessment of Human Exposure to Environmental Pollutants"; Martinus

Nijhoff Publishers: The Hague, the Netherlands, (1979).

2. Luepke , N. -P., Ed. "Monitoring Environmental Materials and Specimen

Banking"; Martinus Nijhoff Publishers: The Hague, the Netherlands, (1979).

3. Lewis, R.A.

Stein, N. ; Lewis, C.W., Eds. "Environmental Specimen Banking

and Monitoring as Related to Banking"; Martinus Nijhoff Publishers: The

Hague, the Netherlands, (1984).

4. Wise, S.A. and Zeisler, R. , Eds., International Review of Environmental

Specimen Banking, NBS Spec. Publ. 706, U.S. Government Printing Office,

Washington, DC, (1985).

5. Wise, S.A., Zeisler, R. , "The Pilot Environmental Specimen Bank Program"

Environ. Sci. Technol., 18, 302A (1984).

3
Trace Analyses and Quality Assurance for Extractable

Organics Chemicals

William D. MacLeod, Jr.

Northwest and Alaska Fisheries Center

The marine environment for decades has been a dumping ground directly or indirectly for a host of chemicals. The National Oceanic and Atmospheric

Administration (NOAA) has long been interested in the extent and impact of this

contamination on our Nation's living marine resources. Last year, NOAA

launched a nationwide study of coastal contamination with its "National Status

and Trends Program for Marine Environmental Quality" (NS&T) . Central to this

multi-million dollar program is the need to known which key chemicals

contaminate our marine environment and what are their trends. It is most

important that this knowledge be of such quality that it can be used with

statistical confidence in helping to understand the nature and extent of

chemical pollution both locally and nationwide. This section deals with

analyses and quality assurance (QA) for the extractable toxic organic chemicals

under the NS&T Program.

For many reasons, analytical procedures for extractable toxic organics

need to be sensitive, down to parts -per-billion (ppb) and sometimes lower. At

the same time, these procedures also must meet standards of reliability.

Generally speaking, such procedures must be performed with painstaking care by

skilled and experienced laboratory personnel on sophisticated analytical

instruments. Often acceptable reliability (Horwitz, et al . 1980) may be

attained at the desired sensitivity only with the best of efforts.

Unfortunately, in the community of marine environmental research, analyses for

trace organics have not always been practiced to uniform professional

analytical standards. To address such deficiencies, two years ago the American

Chemical Society issued its "Principles of Environmental Analyses" (Keith, et

al. 1983), giving special emphasis to QA. Related to this action, last year

NOAA launched a QA program for its NS&T Program.

At NOAA's National Analytical Facility (NAF) , we have been involved in the

analyses and QA for extractable organics. Our laboratory manual (MacLeod, et

al . 1985) provides NS&T with detailed and standardized analytical procedures

for the extractable organics. This manual is now in its second edition as NOAA

Tech. Memo. NMFS F/NWC-92, which supersedes the earlier version (MacLeod, et

al . 1984). We also prepare the GC calibrating and internal standards for the

extractable organic chemical contaminants, an the reference sediments and

tissues used to monitor laboratory performance.

The procedures described in the manual are lengthy and detailed for a number of reasons. This is largely due to the complex mixtures of extractable

organic compounds that marine environmental samples often contain. To be

effective, an extraction and cleanup procedure must separate numerous naturally

occurring compounds from the toxic organic analytes of interest. Figure 1 demonstrates difficulties that can be encountered in an analysis of a marine

sediment. The upper portion is the gas chromatogram of the aromatic hydrocar

-

4
bon fraction after what was once regarded as adequate cleanup by liquid

chromatography. In the figure, each upscale deflection is the result of one or more organic compounds reaching the instrument's detector and giving a measurable response at a given point in time. Obviously, if more than one compound

enters the detector at the same time, analyte quantitation may be seriously

compromised.

To remove the interfering compounds, we developed an additional cleanup

step (Ramos and Prohaska, 1981) which reduces the complexity of the upper

chromatogram to the more tractable mixture shown in the lower chromatogram.

The analytes of interest are denoted by numerals and listed in the legend.

While some extraneous compounds remain in the lower chromatogram, few of them

now interfere with the measurement of the analytes of interest. Other techniques described in the manual are depicted in the flow chart shown in Figure

2. Most of these are relatively well known and need no further discussion

here, except to point out that they are essential, which of course makes the

overall procedure lengthy.

In any discussion of quality assurance and methodology, consideration

should be given to what can be accomplished when the proper analytical principles are observed irrespective of the particular analytical method followed.

Figure 3 shows a comparison of results from an earlier NOAA sponsored study

(MacLeod, et al . 1982). Participating laboratories were free to use their own procedures. The upper portion is a graph of the aromatic hydrocarbons found by

another marine research laboratory. The lower portion is a graph of our own

results on the same reference material. In this instance, the results were

remarkably similar, even though each laboratory used a different approach.

That's the good news. The bad news is that this is the only example of its

kind we have encountered in more than five years of interlaboratory comparisons

with more than thirty laboratories.

We felt that more rigorous control of the many variables was needed.

Quality assurance under NOAA's NS&T Program provided us with an opportunity to

test such an approach. It began last year with the "National Benthic Surveillance Project," a nationwide component of NS&T conducted by the National Marine

Fisheries Service (NMFS). Two other NMFS laboratories are involved, one under

the Southeast Fisheries Center in Charleston, South Carolina, and the other

under the Northeast Fisheries Center in Gloucester, Massachusetts. Chemists

from these NMFS labs expressed interest in employing the analytical procedures

we had found useful over the years. For our part, we undertook to describe

these procedures in the detailed format now published (MacLeod, et al. 1985)

and to manage interlaboratory comparisons . Thus , the NMFS labs went forward

with a common approach to the analyses for extractable toxic organics.

Specifically, the NMFS labs used the following:

- The same detailed methods manual

- The same checked and approved reagents

- The same calibration standard solutions

- The same internal standard solutions

- The same reference materials

We believe that the establishment of such a common, validated approach

5
nationwide is a significant advance in the analysis of extractable toxic

organics in the marine environment. In these analyses, the following QA

measures are specific in the lab manual.

- Frequent Calibration Check of GC Performance

- Internal Standards for: (a) Extraction, (b) GC

- Blank Analyses

- Spiked Blank Analyses ("Reagent Spike")

- Blind Duplicate Analyses

- Reference Materials Analyses

We are now in the process of comparing results from the NS&T laboratories

and determining whether environmental analytical data for extractable organics

can be compared nationwide on a common basis. The bottom line for QA is the

comparison of analyses of reference materials between various labs. Tables 1 through 3 contain analytical results from the NMFS laboratories on the Duwaraish

III reference sediment. There hasn't been time to conduct a thorough statistical examination of these data, but preliminary inspection of the data

suggests that they may be more consistent than those found in our earlier studv

(MacLeod, et al . 1982) involving analyzes of Duwamish I and II reference

sediments. Should this prove to be statistically true, it would represent an accomplishment, in view of the divergent prior experience in these kinds of

analyses by the NMFS labs

References

Horwitz, W. , L.R. Ramps, and K.W. Boyer, 1980. Quality Assurance in the

Analysis of Foods for Trace Constituents , J. Assoc. Off. Anal. Chem. 63,

1344-1354.

Keith, L.H. , W. Crummet, J. Deegan, Jr., R.A. Libby, J.K. Taylor, and G.

Wentler, Principles of Environmental Analyses, Anal. Chem. 55, 2210-2213

(1983).

MacLeod, W.D., Jr., P.G. Prohaska, D.D. Gennero, and D.W. Brown, 1982,

Interlaboratory Comparisons of Selected Trace Hydrocarbons from Marine

Sediments, Anal. Chem. 54, 386-392 (1982).

MacLeod, W.D., Jr., D.W. Brown, A.J. Friedman, 0. Maynes , and R.W. Pearce,

Standard Analytical Procedures of the NOAA National Analytical Facility.

1984-1985; Extractable Toxic Organic Compounds, NOAA Technical Memorandum

NMFS F/NWC-64, 110pp. (1984).

MacLeod, W.D., Jr., D.W. Brown, A.J. Friedman, D.G. Burrows, 0. Maynes, and

R.W. Pearce, C.A. Wigren, and R.A. Bogar, Standard Analytical Procedures

of the NOAA National Analytical Facility, 1984-1985: Extractable Toxic

Organic Compounds, Second Edition, NOAA Technical Memorandum NMFS F/NWC92, 121 pp.

Ramos, L.S. and P.G. Prohaska, 1981, Sephadex LH-20 Chromatography of Extract.;

of Marine Sediment and 3iological Samples for the Isolation of Polynuclear

Aromatic Hydrocarbons, J. Chromatog. 211, 284-289.

6
Table 1. Mean concentrations (n=3) in ng/g dry weight cf selected aranatic hydrocarbons

found in reference sediment: Cuwamish III. Relative standard deviations

expressed as a percent of mean are shown in parentheses. NAF » Jlaticnal

Analytical Facility, ME - Northeast Fisheries Center, SE = Southeast Fisheries

Center

Ccnpcund NAF Chen. 1 NAF Chen. 2 NAF Chen. 3- ME SE

napthahalene 320 (11) 320 (15) 420 (18) 250 (21) 330 (11)

2 - metbr/lraphthalene 160 (17) 150 (4) 200 (33) 110 (19) 180 (6) 1 -iiethytyaphthalene 120 (16) HO (5) 150 (32) 80 (16) 150 (3)

biphenyl 39 (13) 21 (7) 37 (23) 31 (8) 57 (7)

2,6- dime t±yInaphdnalere 70 (10) 75 (7) 78 (16) 58 (15) 76 (4)

acenaphthens 300 (22) 310 (8) 300 (2) 290 (16) 420 (9)

fluorene 310 (3) 330 (5) 330 (9) 290 (18) 430 (10)

phenanthrene 2300 (8) 2300 (7) 2400 (5) 2200 (9) 3200 (6)

anthracene 510 (3) 590 (9) 550 (2) 650 (16) 730 (2)

] 1-methylp'nenanthrene 220 (11) 220 (7) 220 (5) 410 (52) 320 (10)

fluoranthene 39CO (9) 4000 (6) 3900 (4) 3700 (4) 5600 (7)

pyrene 4100 (5) 4400 (3) 4200 (4) 3900 (5) 5300 (6)

benz [a] pyrene 1500 (7) 1900 (8) 17C0 (3) 1400 (5) 2100 (10)

chrysene 2600 (7) 3800 (15) 2700 (4) 2100 (7) 3600 (6)

benzo[e]pvrene 1600 (4) 2000 (8) 1700 (3) 1400 (5) 2000 (9)

benzo [ aj pyrene 1800 (3) 2200 (3) 1800 (3) 1700 (7) 2700 (6)

perylene 510 (2) 640 ( 5) 550 (5) 460 (8) 710 (5)

1 dibenz [ a , h] anthracene 310 (4) 470 (11) 280 (2) 310 (5) 430 (7)

! Table 2. Mean concentrations (n»3) in ng/g dry weight of selected chlorinated

canpounds found in reference sediment: DLiwamish III. Relative standard

deviations expressed as a percent of mean are shown in parentheses. NAF -

National Analytical Facility, NE - Northeast Fisheries Center, SE -

Southeast Fisheries Center

Ccnpound NAF Chen. 1 t&F Chen. 2 NAF Chen. 3 NE SE

i hexachlorobenzene *0.4(36) <0.9 <0.4(7) 0.6(14) 32(26)

lindane (gamna-EHC) <0.2 <0.6 <0.3 <0.6 <1

heptachlor <0.4 <1 <0.5 <0.7 O

aldrin <0.3 <0.7 <0.4 <0.6 <2

heptachlorepoxide <0.3 <1 <0.5 <0.8 <2

alpha-chlordane 0.9(3) 2(22) 1(13) 2(11) 2(3) trans -nonachlor 0.4(1) 0.6(27) 0.4(7) 0.9(17) <1

dieldrin <0.3 <1 <0.5 0.7 <2

mirex <0.4 <1 <0.6 0.8 <2

o,p' -DDE <0.4 <1 <0.6 <L <3

p,p' -DDE 7(H) 9(16) 7(4) 10(37) 9(6)

o,p'-DDD 4(2) 5(21) 4(5) 8(39) 7(8)

, p.p'-DED 15(7) 20(25) 16(9) 27(92) 21(10)

o,p' -DDT 4(16) 5(22) 4(11) 5(35) <2

p.p'-ddt <0.5 <1 <0.7 10(83) <2

I

i

“?
CJ

10

Table 3. Mean concentrations (n=3) in ng/g dry weight of polychlorinated biphenyl standards found in

reference sediment : Duwamish III. Relative standard deviations expressed as a percent of mean

are shown in parentheses . NAF =» National Analytical Facility, NE = Northeast Fisheries Center,

SE = Southeast Fisheries Center.

Compound NAF Chan. 1 NAF Chan. 2 NAF Chan. 2 NE SE

2,4'- dichlorobiphenyl <1 <4 <2 <3 <3

2,5,4'- trichlorobiphenyl 23 (7) 29 (14) 25 (2) 23 (10) 32 (19) 2 , 4 , 2

' , 4 ' - tetrachlorobiphenyl 8 (13) 13 (44) 11 (14) 9 (7) 14 (ID

2 , 4 , 5 , 2

' , 5 ' -pentachlorobiphenyl 70 (20) 85 1

1

CTs 77 (9) 64 (14) 63 (3)

2, 4, 5, 2' ,4'5' -hexachlorobipherxyl 110 (20) 140 /

s rH 00 120 (30) 77 (10) 72 (4)

2, 3, 4, 5, 6, 2' ,5' -heptachlorobiphenyl <0.4 <0.6 <0.1 5 (30) <2

2, 3, 4, 5, 2' ,3' ,4' , 5 ' -octachlorobiphenyl 3 (27) 12 (30) 11 (16) 17 (51) 9 (10)

2, 3, 4, 5, 6, 2', 3', 4' ,5' -nonachlorobiphenyl 10 (52) 12 (0) 10 (17) 17 (48) 7 (11)

8
Time (min.)

0

50° 50° Temp. (° C)

Figure

i

10 20 30 40 50 60 70

_l ,1 H H 1 T

, J100° 150° 200° 250° 280°

1. Gas chromato gran of an intertidal sediment extract following

chromatographic clean-up with (a) silica gel and (b) silica gel,

followed by Sephadex LH-20 using cyclohexane-methanol-dichloromei_hane (Ramos & Prob.aska, 1981). Labelled peaks are: I.S. « internal standard; 1 — naphthalane; 2 - methylnaphthalenes ; 3 — biphenyl, 4 *> dime thylnaphthalenes ; 6 — fluorene; 7 ** phenanthrene ; 8 — methylphenanthrenes ; 9 - dimethylphenanthrenes ; 10 - fluoranthene; 11 — pyrene; 13 — chrysene; 14 — benzo [ e ] pyrene

;

15 - benzo [a]pyrene; 16 - perylene

9
Tissue

Mix with Na

2 S04 under CH^CIj using Tissumizer, then centrifuge.

I Twice, replace the CH2 CI

2 and re extract

Discard Concentrate and Discard

displace CH 2 Cl

2 with hexane

Sediment

Tumble with l\la 2 S04

in CH3 CI

2

I Twice, replace the CH,CI„

and re extract

Concentrated extract

in hexane

Chromatographic separation on silica/alumina

Possible analysis by GC

with ECD detection Chromatographic separation on Sephadex LH 20 GC anelytii with FID and/or MS

detection

Possible analysis by GC

with ECD detection GC analysis with FID, ECO and/or MS detection

Figure 2. Summary of the Standard Analytical Procedures

Analytical Facility (MacLeod, et al. 1985)

of NOAA's National

10
200 -

! SET D

j Method 1

2000 r

T

|

I I I

i i 1

9 10 11 12 13 14 15 16 17 18

CD

i_ 200 r

c NAF

0Jo

] Method 2 c r o l o

l

2000 s

1000 ;

O'—

9 10 11 12 13 14 15 16 17 18

| Figure 3. Bar graphs of selected aromatic compounds found in Duwamish II

reference sediment (MacLeod, et al. 1982). Means (n=*3) and

standard deviations shown for another marine science center (set

D) and our laboratory (NAF) . Compounds: 1 - naphthalene; 2 -

2 -methylnaphthalene ; 3 - 1-methylnapthalene ; 4 - biphenyl; 5 -

2 , 6 -dime thylnaphthalene ; 6 - 2 , 3 , 5- trimethylnaphthalene ; 7 = fluorene; 8 - dibenzo thiophene ; 9 - phenanthrene ; 10 - anthracene; 11 - 1-methylphenanthrene ; 12 - fluoranthene; 13 - pyrene;

14 - benz [ a] anthracene ; 15 - chrysene; 16 - benzo[e]pyrene; 17 - benzo[ a] pyrene; 18 - perylene

11
Intgyconvparison for Trace Metals in Marine Sediments

S . Berman

National Research Council, Canada

Four samples of marine sediments were prepared. These were

essentially aluminum silicate materials typical of northeast coastal

sediments. The sediments had been freeze dried, screened through 100

screens, homogenized and bottled. Homogeneity tests in this laboratory

involving the elements Al , Si, Mn, Fe, Cu, Zn, Cd, Hg and Pb showed no significant differences between bottles and intrabottle precision between

replicate samples to be no worse than the precision expected from the

analytical procedures involved at the particular concentrations concerned.

The four samples consisted of two pairs, each with generally similar

trace metal contents.

Samples were sent to the six participants in the late summer and early

fall of 1985. The deadline, determined by the date of this workshop, and

the lateness in receiving the names of the participants allowed only six to

nine weeks for the determination of seventeen elements in the four

sediments, each done on four replicate samples. It is hoped that future

intercomparisons can be conducted on a somewhat more leisurely basis. To

the credit of the participants, all submitted most of what was required

from them.

A preliminary survey of the results (a final report will be issued by

early spring, 1986) shows that, in general, the laboratories don't have

problems with essential trace metals such as Cu, Zn, Cd, Hg and Pb

.

There is concern regarding the analyses for the major components, Al,

Si, and Fe. The problems with these three may be in the sample

decomposition or in matrix problems connected with their determination by

flame atomic absorption spectrometry. The fact that a trace method is

being used for a major concentration obviates the precision (and accuracy?)

of traditional classical procedures. The one laboratory which used x-ray

fluorescence spectrometry achieved acceptable values only for iron,

indicating calibration problems.

There is some disappointment regarding results for manganese, nickel

and arsenic. At the concentrations involved, a better precision was expected. The other six elements (Se, Ag, Sn, Sb , Ti and Bi) are present

in very low concentrations. There is no doubt that some of the laboratories can analyze for these, but as there are no definitive values yet

available there is not much to be said.

This laboratory is attempting to assign reliable values for most of

the elements concerned in this study. The results will be reflected In zhe

final report.

The results were discussed in detail in the inorganic analysis

sessions. These discussions, I feel, were productive with much valuable

deedback to the laboratories and the coordinator.

12
A Statistical Review of Interlaboratorv Comparison Data

Robert C . Paule

National Bureau of Standards

The following comments apply to the requirements for organizing an interlaboratory study, and for analyzing the data. The statistician and

the coordinating scientist each bring specialized information to a successful study. In the planning stage, the scientist provides general information on what the field can do, and the statistician provides information on

the types of answers that can be obtained.

Care should be taken in an interlaboratory study in the choice of

materials to be sent to the laboratories. Homogeneous materials should be

supplied at several levels for the analytes of interest, and they should

have realistic interferences. The laboratories should be chosen to

represent the laboratory population of interest.

Some of the answers obtainable from an interlaboratory study are: the

average values for the test materials; the standard deviations for the

average values; the standard deviation for a single laboratory measurement;

and the within- and between- laboratory components of standard deviation.

An interlaboratory study frequently gives a better understanding of the

measurement process and indicates areas for improvement.

A number of increasingly complicated nested experimental designs were

presented. The more complicated designs yield more information, but

require that the laboratory measurements be in better control. Outlier

values, in addition to distorting the averages, also present serious

problems in the statistical analysis, and in subsequent probability

statements. Outliers cause problems in the pooling of variances which are involved in the statistical analysis. For simple designs, reasonable

compromises to the outlier problem sometimes can be made. Outliers,

however, can be disastrous for complicated designs.

Interlaboratory studies that survey the state of the field normally

should have simple designs since there is frequently a noticeable lack of

measurement control. Several examples of survey type interlaboratory

studies were presented.

Finally, the relative merits of graphical vs. quantitative statistical

evaluations were discussed, and several examples were presented.

13
Organic Methods Workshop Summary

S.A. Wise, M.M. Schantz , and W.E. May

National Bureau of Standards

The major focus of the Organic Methods Workshop was to review the

results from the interlaboratory comparison study and to make recommendations for future quality assurance procedures for the NOAA National Status

and Trends (NS&T) Program. Prior to the workshop, samples of wet/frozen

sediment and mussel tissue were prepared by the Northwest National Marine

Fisheries Service (NMFS) and distributed for analysis to the NMFS laboratories, NOAA Mussel Watch contractors (i.e., Battelle New England Marine

Laboratory, Science Applications International Co., and Texas A & M

University) and the National Bureau of Standards (NBS) . These samples were

to be analyzed for the determination of polycyclic aromatic hydrocarbons

(PAH), polychlorinated biphenyls (PCBs) , and chlorinated pesticides.

Results obtained on these samples by the various laboratories were discussed at the workshop. William MacLeod, Northwest NMFS laboratory, presented

a detailed summary of the results obtained by his laboratory and the

Northeast and Southeast NMFS laboratories. All three of these laboratories

are using the analytical methods developed by the Northwest NMFS laboratory

and published as a laboratory manual (1). The three Mussel Watch contractors were requested to also utilize these same procedures. Results for the

sediment analyses from the Northwest NMFS lab showed good intralaboratory

precision for analyses from three different analysts and reasonable

agreement among the three NMFS laboratories. Unfortunately, the levels of

the chlorinated pesticides in the samples were low and many of the reported

values were at the detection limit. Preliminary results also were reported

by the Mussel Watch contractors and by NBS for the sediment sample.

It was the general feeling of the contractors that they needed

additional time to implement adequately the required NMFS procedures for

the analyses. Also there was concern expressed by the Mussel Watch

contractors regarding the need to implement the NMFS procedures exactly as detailed in the reference manual. A number of technical questions were discussed regarding the analytical procedures. Concern was expressed by

several participants that the required use of the NMFS procedure by all of

the laboratories involved in the program may result in precise data, but

that NOAA would be unable to determine whether the results were accurate.

There should be a means to validate the accuracy of this procedure. It was pointed out that the NBS values for the PAH, which were obtained by

somewhat different methods, were in reasonable agreement with the data

obtained by the NMFS procedures.

The NMFS procedure calls for the use of 3 g of tissue as the required

sample size. It was suggested by the Mussel Watch contractors that this b<- increased to 10-20 g. This larger sample size would allow greater sensitivity for the determination of the compounds of interest. This suggestion

was adopted by NOAA.

Methods for the quantification of PAH and pesticide residues appear to

be well-developed; however, there is need for improvement in the methods

14
for quantification of PC3s . Questions regarding the basis to be used for

the quantification of PCBs were raised, e.g., should total ?C3s be quantified or individual PCS congeners; which congeners should be used to

represent a specific group of ?C3s with the same number of chlorine atoms?

The individual congeners specified in the NMFS procedure for quantification

were selected based on availability. The selection of more suitable

congeners based on occurrence in the samples should be investigated.

There was an extensive discussion of the need for reference materials

for marine tissue and sediment for use as control materials and in the

validation or methods. MBS suggested that a series of different reference

materials of varying complexity could be prepared, e.g., a sediment

extract, cod liver oil to simulate a tissue extract, and frozen or dry

sediment and tissue samples with either certified or "benchmark values".

It was thought that the sediment extract might be unstable. A cod liver

oil SRM will be available from NBS in late 1986 with certified values for

selected pesticides and information values for PCBs and PAHs . Reference

materials for the determination of PCBs and PAHs in sediment (air dried)

are available from the National Research Council in Canada.

Conclusions and Recommendations

1. The laboratories involved in the NOAA NS&T Program are reasonably

comfortable with using the NMFS procedure if they have some latitude

in the making of modifications, i.e., there needs to be a mechanism

for implementing changes to the procedure and validation of those

changes. This woald allow for improvement of analytical methods

throughout the duration of the NS&T program rather than freezing

existing methodology.

2. Because of the concern that all the laboratories would be using the same procedure and, therefore, a possible bias could exist in the data

base generated, some validation of analytical methods should be

implemented by other laboratories and/or methods. NBS could serve

this function since they are using different analytical methods for

their analyses on selected specimens and on the intercalibration

materials

3. The following recommendations were made concerning future

intercalibration studies:

a. Statisticians should prepare a design for future round

robins (R. Paule of NBS would be willing to work with NOAA

on the design)

b. Appropriate existing materials for use in such round robins

should be identified.

c. The appropriate round robin coordinator should be selected and

the participants identified. Participants in addition to the

NMFS labs and the Mussel Watch contractors should be solicited.

15
d. Results should be evaluated and returned to the participants.

e. Benchmark values for the intercalibration materials, derived

from the round robin study, should be determined and provided to

the laboratories after the study.

4. The methods for quantification of PCBs should be re-examined and

improvements suggested. The criteria for the selection of representative PCB congeners for quantification should be examined.

5. A mechanism should be established to identify research needs and

concerns relevant to the NS&T program.

REFERENCE

1. W. D. MacLeod, Jr., D. W. Brown, A. J. Friedman, D. G. Burrows, 0.

Maynes , R. W. Pearce, C. A. Wigren, and R. G. Bogar, Standard Analytical Procedures of the NOAA National Analytical Facility, 1985-36,

Extractable Toxic Organic Compounds, 2nd ed.

,

National Marine

Fisheries Service, Seattle WA (1985).

16
INORGANIC METHODS WORKSHOP SUMMARY

T. C. Rains

National Bureau of Standards

Dr. Shier 3erman opened the discussion by reviewing the

interlaboratory data presented earlier in the day. From the data presented, it was quite obvious that major problems existed in the determination

of the 17 elements in estuarine sediments, No's A, 3, C, and D. Some

attendees expressed the opinion that different methods of sample preparation may have contributed to the wide variation in the results . The

preferred sample preparation would be to have just one dissolution procedure for the determination of all 17 elements. Since As, Se, Hg, Si ; Al,

and etc. are being requested in a wide variety of matrices and concentration, it would appear that no one method could be used to prepare an estuarine sediment for the determination of all the elements of interest.

Then the question arose, if dissolution is the major problem, why not

submit a solution of an estuarine sediment together with the samples for

the next evaluation? Any differences in measurements would confirm sample

digestion as the source of error. The response from the attendees to this

question was mixed.

The question of what range of precision and accuracy is acceptable was

raised. Only NOAA can answer that question, and the NOAA representatives

present were not able to give exact values, but only stated a desire to

have state-of-the-art precision and accuracy.

The sample size was discussed. From the discussion, it became

apparent that the contract laboratories were using 10-100 mg test portions

in a pressure vessel. This small sample size is sure to lead to a wide

variability in the results since the homogeneity of the sediments are not

known at this level. Shier Berman suggested using 250 mg as a minimum

sample weight. The discussion that followed indicated that the method

being used by the contract laboratories is as follows: 10-100 mg in Teflon

pressure vessel, addition of HF and HNO 3

, heat for 2 hours, cool, add H3 BO3 and proceed with the analysis by ICP or AAS . Any remaining solids were

ignored. For the one or two laboratories using HF, HNO 3

, and HCIO4 in an open beaker, As, Se, Cr, and Si are sure to be low. CRC and NBS representatives suggested that at least three dissolution procedures be used.

Samples for As and Se should be dissolved under reflux conditions, Si by a basic fusion and the remaining elements by HF, HNO 3 , and HCIO^ digestion.

The 5-10 percent carbon should be destroyed before analysis.

The question of precision was raised again. It was generally agreed

that 10 percent should be adequate for the trace elements, but 1-2 percent

was needed for the majors such as Si, Fe, and Al . This higher degree of

precision for the majors is essential since the trace elements are being

ratioed to the major elements.

A plea was made for four different types of sediments (high-organic

with "15-20% organic material, carbonate, Al/Si base, and Si02 ) . As an

17
example, Che sediments from Baltimore harbor after drying will burn. A

strong recommendation was made for the preparation of the above four types

of sediments to be used as controls

.

Another potential problem arose during the discussion, namely that of

making multiple-dilutions for the determination of the major elements by

ICP. The data presented by Shier Berman showed 25-40 percent variation,

yet each laboratory stated that they can do 2-3% precision for the majors.

Also, a precise value doesn't always mean an accurate value.

X-ray technique had problems in calibration. Standards for the

various matrices could be of help to the technique.

While the negative aspects were discussed at length, on the positive

side, Zn, Cu, Pb , and Cd were being determined at an exceptional level.

When limits of detection (LOD) are reported, NOAA wants to know how

the LODs are determined. Shier Berman will send to each laboratory a document explaining how to calculate LOD.

The subject of tissue was raised. In general, the attendees agreed to

hold the tissue sample until a round-robin set has been analyzed. These

samples should be available in late March or April.

18
Long-Term Goals*

John K. Taylor

National Bureau of Standards

If expectations (of users) are not met ? then all of the debates,

the round-robin tests, the committee and task-group work, and

lofty statements of involvement with quality and commitment to

excellence have not been productive.

The user of data must have accurate results otherwise they will have

limited if any value and even may be misleading and engender erroneous

conclusions. The long-term (and short-term) goals of every laboratory

reporting data should be to always get accurate results.

If the "same" result cannot be obtained on the same sample at

various times or situations, what confidence can anyone have in

any result, and what confidence can anyone have in results on different samples?

The indicators for sameness and accurate results are precision and bias

which must be evaluated continually. Appropriate evaluation samples, used

consistently and the results control charted are the best indicators of the

stability of a measurement process. When evaluation samples are characterized accurately (reference materials) bias can be evaluated as well. Every

laboratory reporting data must have its own estimation of its measurement

uncertainty and have documented evidence to support it. This is the first

requirement that must be met in order to report data. This may be called

INTERNAL CONFIDENCE.

After, and only after INTERNAL CONFIDENCE is established, a laboratory

should seek EXTERNAL CONFIRMATION of its internal evaluation of measurement

uncertainty. This may reveal unsuspected bias (which is difficult for a laboratory to evaluate in isolation) but there should be no discrepancies

between internal and external estimates of precision.

EXTERNAL CONFIRMATION of measurement quality is best achieved by the

use of appropriate certified reference materials. Round robins are useful,

and are especially so when certified reference materials are not available.

However, the samples used in round robins should simulate the normal test

samples more closely than any available reference material.

*This paper was on the program but was not presented, due to time

limitations

.

19
The requirements for round-robin samples are essentially the same as those for reference materials. They must have

•close matrix match

•sufficient homogeneity

and they should be

•accurately characterized

The first requirement is necessary if inferences are to be made on test sample performance from round- robin performance. The second is

necessary to distinguish measurement variance from sample variance.

Because precision can be evaluated satisfactorily from the on-going

measurements of a laboratory, the primary function of a round-robin should

be to evaluate accuracy, hence the samples should be characterized

accurately. Homogeneous uncharacterized materials can qualitatively

identify that bias exists between laboratories but they cannot be used to

quantitatively evaluate bias. Accordingly, sufficient work should be done on the samples to elevate them to reference material status , to the extent

possible

Round- robins are of limited use unless the resulting data are critically analyzed. Appropriate corrective actions should be sought for

each problem discovered otherwise the exercise has been futile.

After a laboratory has established INTERNAL CONFIDENCE and EXTERNAL

CONFIRMATION of the quality of its data for evaluation samples, it must

perform all of its measurements using appropriate quality assurance

procedures so that quantitative limits of uncertainty can be reported for

all of its data. This requires

•Use of appropriate methodology

•Adequate calibration

•Proper application

•Maintenance of statistical control

Quality assurance is not a one-time effort but a continuing activity. The

goal must be elimination of defects. It is a never ending effort to

improve quality and productivity. Only by continuous and diligent effort

will a laboratory achieve its goal to always get accurate results.

Monitoring programs can achieve their goals only as the individual

laboratories achieve their goals. Intercalibration exercises are necessary

but their purpose should be EXTERNAL CONFIRMATION. More effort needs to be

expended on the development of suitable certified reference materials so that laboratories can have INTERNAL CONFIDENCE for all of their data.

20
RECOMMENDATIONS

• Laboratories Must Attain Statistical Control

• Laboratories Must Constantly Demonstrate Maintenance of

Statistical Control

• Control Charts Can Provide Best Evidence for Both

• Use Internal Reference Materials to Determine Stability

• Use Certified Reference Materials to Demonstrate Accuracy

• Use Both in Control Chart Mode

• Use Control Charts of Duplicate Measurements of Actual Samples to Monitor

On-Going Precision

• For Practical Purposes IRM'S and Duplicate Samples Must Bear the Burden

of Monitoring Statistical Control

• Well Chosen Generic CRMS Should be Used to Monitor for Accuracy

21
Certified Reference Materials Currently Available for

Use in NOAA Programs*

Willie E. May

The increasing requirements for accuracy in chemical analysis and the

necessity to interrelate and combine data sets from several laboratories or from the same laboratory over time have created a need for well-characterized, stable reference materials [1]. Reference materials of various types

may be utilized for calibrating and/or determining the performance of

analytical instrumentation and validating analytical methods and

procedures

.

In 1977 the International Organization for Standardization (ISO)

defined a reference material (RM) as "a material or substance one or more properties of which are sufficiently well established to be used for the

calibration of an apparatus or for the modification of a measurement

method". A certified reference material (CRM) was defined as " a reference

material accompanied by, or traceable to, a Certificate stating the

property values concerned, issued by an organization, public or private,

which is generally accepted as technically competent" . The National 3ureau

of Standards (NBS) issues Standard Reference Materials (SRMs) which are a special class of CRMs that have been carefully analyzed and certified by

NBS.

SRM's that are available from NBS and appropriate for use in the

analysis of marine samples are provided below along with a brier description of each. Certificates of Analysis for each are provided in Appendix C. A complete compilation of CRM's available from other International

standards organizations can be found in "Available Standards for Use in the

Analysis of Marine Materials" by David Russell [2]

.

NBS CALIBRATION SOLUTIONS (ORGANIC)

Organic calibration solution SRM's are intended primarily for

establishing chromatographic retention times and determining instrument

response factors for the compounds included in each. They may also be used

to fortify samples with known amounts of the certified compounds included

(e.g. for recovery studies or quantitation based on the method of standard

additions)

* 1583 Chlorinated Pesticides in Isooctane

Certified concentration values for four and information

value for one chlorinated pesticide.

*This paper was on the program but was not presented due to time

limitations

.

22
* 1585 PCB Congeners in Isooctane

Certified concentration values for eight chlorinated

biphenyl congeners.

* 1586 Isotopically Labeled and Unlabeled Priority Pollutants in

he thano

1

Separate solutions of both Labeled and unlabeled compounds

Certified concentration values for the ten components in one solution are for compounds with either a deuterium or carbon- 13 label. The same compounds are certified in the

other solution except that they contain no isotope other

than those naturally occurring.

* 1614 Dioxin (2 , 3 , 7 , 8 -TCDD in Isooctane)

Separate solutions with certified concentration values

for carbon- 13 labeled and unlabeled 2 , 3 , 7 , 8 -TCDD

.

* 1647 PAH in Acetonitrile

Certified concentration values for the 16 PAH on the EPA

list of priority pollutants.

NBS CALIBRATION SOLUTIONS (INORGANIC)

These aqueous solutions are intended primarily for use in atomic

absorption, optical emission spectrometry, spectrophotometry, or any other

technique that requires aqueous solutions for calibration. These SRM's may

also be used as primary standards for verifying the accuracy of secondary

and laboratory standards.

* 1641

* 1642

* 1643B

Mercury in Water (/xg/mL)

Mercury in Water (ng/mL)

Trace Elements in Water

Aqueous solution of 18 elements, each at ng/mL

concentrations

.

* 2121-2129 Spectrophometry Standard Solutions

Each SRM in this series contains four single element

solutions contained in individual bottles.

NBS NATURAL MATRIX MARINE SRM's

* 1566 Oyster Tissue (in preparation)

This material will issued freeze-dried and will have

certified values for selected trace elements. Information

values (by one technique only) will be provided for

selected chlorinated pesticides, PCB congeners, and PAH if

present in measurable concentrations.

* 1588 Cod Liver Oil (to be available in Nov./87)

This material is intended for use as a surrogate for a

23
marine tissue SRM and will have certified values for

organic constituents. Certified concentration values will

be provided for selected chlorinated pesticides, PCS

congeners, and PAH.

* 1646 Estuarine Sediment

This material has certified concentration values for a number of trace elements of nutritional and toxicological

significance

FUTURE REFERENCE MATERIALS NEEDS

It was the consensus of the attendees that the certified reference

materials of most urgent need were a tissue homogenate and a natural

sediment( preferably wet/frozen) with certified concentration values for

selected chlorinated pesticides, PC3 congeners, and PAH. Reference

Materials currently exist that are appropriate for use in providing quality

assurance for trace element analyses of similar matrices.

References

[1] Taylor, John K.,'' Reference Materials -What They are and How They Should

be Used", Proceedings of the Symposium on Reference Materials and Their

Use in the Nuclear Fuel Cycle, Aug. 8, 1982, Knoxville, TN.

[2] Russell, D. S., "Available Standards for Use in the Analysis of Marine

Materials", Report No. 8, NRCC No. 23025, Marine Analytical Chemistry

Standards Program, National Research Council of Canada.

24
APPENDIX A

NOAA/NBS Quality Assurance Workshop

National Bureau of Standards

Gaithersburg, Maryland

AGENDA

Thursday, December 5, 1985

Registration 8:30 - 9:00 am

Session I 9:00 am, Building 221, Room B165

John K. Taylor, Presiding

Welcome Harry S . Hertz

Director, Center for Analytical

Chemistry, NBS

Introductory Remarks John A. Calder

Ocean Assessments Division, NOAA

Willie E. May

Chief, Organic Analytical

Research Division, NBS

The Role of Specimen Banking in the

NOAA Status and Trends Program

Rolf Zeisler

Preparation and Analysis of

Interlaboratory Comparison Samples

William MacLeod, Shier Berman

Comments on Interlaboratory

Comparison Data

Robert Paule

12:45 p.m. Lunch, SR Lunch Club

Thursday, December 5, 1985

2:00 p .m.

Session IIA. Organic Methods Workshop Building 221, Room B165

Stephen A. Wise, Presiding

a. Review of Interlaboratory Data

b. Critical Evaluation of Analytical

Methods Used in NOAA Program

Session IIB. Inorganic Methods Workshop Building 220, Room A340

Theodore C. Rains, Presiding

a. Review of Interlaboratory Data

b. Critical Evaluation of Analytical

Methods Used in NOAA Program

7:00 pm Social Hour

Sir Walter Raleigh Inn

7:30 pm Dinner

25
Friday, December 6, 1985

9:00 a.m.

Session III Building 221, Room B165

Willie E. May, Presiding

Organic Methods Workshop Summary Stephen A. Wise

Inorganic Methods Workshop Summary Theodore C. Rains

Long-Term Quality Assurance Goals and

Practices Accuracy & Precision Goals

John K. Taylor

NBS SRM's Currently Available for

Use in NOAA Program

Willie E. May

Future Reference and Standard

Reference Material Needs

Willie E. May, Discussion Leader

12:30 p.m. Lunch, Dining Room C

Friday, December 6, 1985

2:00 p.m.

Session IV Building 221, Room B165

John A. Calder, Presiding

Protocols for Future Round-Robin

Exercises

Robert Paule

Protocols for Sampling Rolf Zeisler

Closing Remarks John A. Calder, Willie E. May

26
FORM MOT- MU

(U-4C) APPENDIX B

U.S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OR STANDARD*

WASHINGTON, D.C. 20234

552-86-009

REPORT OF ANALYSIS

NOAA INTERCALIBRATION SEDIMENT

Submitted to:

John A. Calder

Gunner Lauenstein

Ocean Assessment Division

National Oceanic and Atmospheric Administration

Three samples of D-3 sediment were received October 9, 1985 from the National

Marine Fisheries Service (NMFS) Laboratory, Seattle, WA. These samples had

been homogenized and bottled by the NMFS laboratory. The samples were kept

frozen at -20°C until preparation for analysis.

For analysis, a sample of four to five grams of wet sediment was weighed to the

nearest tenth of a milligram. The weighed sample was placed in a mortar

containing approximately ten grams of sodium sulfate and then covered with

another approximately ten grams of sodium sulfate. The sediment plus sodium

sulfate was then ground to "dry 11 the sediment. At this point the sediment and

sodium sulfate were placed in a glass thimble and Soxhlet extracted for sixteen

hours using 200 mL of methylene chloride.

After Soxhlet extraction, the methylene chloride extract was concentrated to

approximately 500/jL using nitrogen gas. The concentrate was then pipetted onto

a precleaned silica Sep-Pak and eluted with 15 mL of 10% methylene chloride in

hexane. The eluent from the Sep-Pak was concentrated to 200|iL for fractionation

by normal-phase liquid chromatography on a semi-preparative aminosilane column

(LC-NH2

).

In the case of the polycyclic aromatic hydrocarbons (PAHs) , the mobile phase

used for LC-NH2 fractionation was 2% methylene chloride in hexane. The alkane

fraction was eluted first and discarded. The aromatic fraction was collected

and concentrated to approximately 500^L for gas chromatographic (GC) analysis

using a flame ionization detector (FID) or liquid chromatographic (LC) analysis

with wavelength programmed spectrofluorometric detection. This approach has

been utilized for the analysis of PAH in several other matrices (1-6).

In the case of the polychlorinated biphenyls (PCBs) and pesticides, the

mobile phase used for LC-NH2 fractionation was hexane for the PCBs and

relatively nonpolar pesticides and 5% methylene chloride in hexane for the more

polar pesticides. These separate fractions were concentrated to approximately

500^L for' GC analysis using an electron capture detector (ECD) . A publication

describing this fractionation procedure is in preparation (7).

I

!l 27
552-86-009

Four samples were analyzed by GC- FID and three samples by LC- fluorescence for

PAHs . Three samples were analyzed by GC-ECD for the PCSs and pesticides. In

the case of the GC-FID analysis, 1-methylpyrene was added as an internal

standard before Soxhlet extraction. For LC- fluorescence analysis,

phenanthrene-d-^g , fluoranthene - d^g , and perylene-d-j^ were added as internal

standards, again before Soxhlet extraction. Finally, for the GC-ECD analysis,

PCS *10 and *198 (2 , 6-dichlorobiphenyl and

2 , 2' , 3 , 3

'

, 4 , 5 , 5

'

, 6-octachlorobiphenyl , respectively) for the PC3 fraction and

perdeutarated DDT for the pesticide fraction were added as internal standards

before Soxhlet extraction. Calibration solutions were also Soxhlet extracted,

concentrated, and fractionated in a manner similar to that for the sediment

samples

.

The GC conditions used for the PAH analysis were:

Column:

Inj ector

:

Sample size:

Injector temperature:

FID temperature

:

Initial column temperature:

Rate

:

Final temperature:

Carrier gas:

Split flow:

Helium make-up gas:

Immobilized nonpolar (DB-5 J&w) fused silica

capillary 30m X 0.25 mm id X 0.25 ^m coating

thickness

Manual, all glass - splitting

2/xL

300° C

300°C

150°C for 2 min

4° /min

280°C for 15 min

Hydrogen at 18 psi

25 mL/min

30 mL/min

For PC3 and pesticide analysis, the same column, injector, and sample size, and

injector temperature were used. The remaining conditions were as follows:

ECD temperature:

Initial column temperature:

Rate

:

Final temperature

:

Carrier gas

:

Split Flow:

Nitrogen make-up:

320°C

180°C with no initial hold

3° /min

270°C for 10 min

Helium at 18 psi

25 mL/min

30 mL/min

The conditions used for LC- fluorescence analysis were as follows:

Column: Reversed- phase octadecylsilane column,

5/um particle size, 4.6mm i.d. x 25 cm

(Vydac 201TP; Lot 540056, No. 20).

Chromatographic Conditions: Linear gradient from 40 % acetonitrile tn

water to 100% acetonitrile in 60 min at

1.5 mL/min; then return to 40% acetonitrile in water in 5 min; remain at

these conditions for 2 min; then stop

flow until next injection.

28
552-36-009

Fluorescence Detection: Detector excitation and emission wavelengths were

programmed as follows:

Time Excitation Emission PAH

(min) (ran) (ran) Determined

0 250 360 Phenanthrene - d]_g

Phenanthrene

19.5 250 400 Anthracene

21.5 285 450 Fluoranthene - d]_Q

Fluoranthene

24.3 330 385 Pyrene

27.0 285 385 Benz [ a ] anthracene

Chrysene

33.8 400 440 Perylene -d]_2

Perylene

37.0 295 405 Benzo [ a] pyrene

Benzo [k] fluoranthene

43.5 380 405 Benzo [ ghi ] perylene

46.5 300 500 Indeno [ 1

,

2 , 3 -cd]

pyrene

Three internal standards were used for the quantification of the PAH as follows: phenanthrene -d-j_o was used to quantity phenanthrene and anthracene;

fluoranthene -d^_o was used to quantify fluoranthene, pyrene, benz [ a] anthracene

,

and chrysene; and perylene -d^Q was used to quantify perylene, benzo [ a] pyrene

,

benzo [k] fluoranthene , benzo [ghi] perylene , and indeno [ 1 , 2 , 3 -cd] pyrene . Detector

response factors were determined using SRM 1647 with perylene and the internal

standards added. Three samples were analyzed with triplicate analyses of each

sample

.

The results of the PAH determinations are summarized in Table 1, and the PC3

and pesticide determininations are summarized in Table 2. Note that the

concentrations are given in terms of dry weight of the sediment. For the dry

weight determination, three samples of approximately 4 grams (each weighed to

the nearest tenth of a milligram) were placed in an oven set at 110°C

overnight. The following morning the samples were reweighed to determine the

weight lost during the drying. The wet sediment was found to contain 45.34%

water

.

As shown in Table 1, the agreement between the GC-FID and the LC- fluorescence

results is good. The anthracene and perylene values are both higher for the GC

analysis which has also been found for the determination of these two compounds

in other types of samples (3-6)

.

The LC values are probably more accurate for

these two compounds since the fluorescence conditions used were both more

sensitive and selective for these compounds. In the case of chrysene, the GC

value includes triphenylene since these compounds are not separable on the

column used.

29
552-86-009

The concentration of the pesticides in this sediment are low as can be seen in

Table 2 ; whereas, the PCSs are at a higher level. This method of fractionation

is convenient for reducing the interferences between the PCB and pesticide

peaks during GC analysis.

Further details and data from these analyses can be found in the notebooks of

M. Schantz #10, pages 1-50 and in S. Wise Notebook- -PAH Measurements, 1986.

Research Chemist

Organic Analytical Research Div.

t sc Organic Analytical Research Div.

Stephen N. Chesler

Supervisory Research Chemist

Organic Analytical Research Div.

Chief

Organic Analytical Research Div.

March 3, 1986

30
552-36-009

Table 1

Concentrations of the PAH in the D-3 Sediment

Compound Concentration (/jg/| ^~a , c k T V J ’ dr

v

weignt)

rrb.c

Phenanthrene 2..42 ± 0,.22 2 .23 4- 0..17

Anthracene 0..71 ± 0 .06 0,.49 + 0..04

Fluoranthene 3..66 ± 0..43 3,.42 + 0..19

Pyrene 3..93 ± 0 .36 3,. 64 + 0..26

Benz [a] Anthracene 1., 34 ± 0,.20

-»L .39 0..11

Chrysene 1..87 21 0.. 1 L -i-Triphenylene 2..70 ± 0 .19

Benzo[e] Pyrene 1

i. «. 86 -f. 0,.10

Benzo [ a] Pyrene 2.. 54 + 0,. 17 2..14 + 0..14

Perylene 0.,77 + 0..04 0..57 + 0.,03

Benzo [k] Fluoranthene 2..14 4- 0.,12

Indeno [1,2,3- cd] pyrene 1..43 4 0.,08

aAverage of 4 extracts, each analyzed 3 times

.Average of 3 extracts each analyzed 3 times

cUncertainty is ±1 standard deviation of the mean.

31
552-86-009

Table 2

Concentrations of the PC3s and Pesticides in the D-3 Sediment

Compound LC Fractiona Concentration'3 > c (ng/g dry weight)

2 ,4' -Dichlorobiphenyl 1 <0.5

2,4' , 5 -Trichlorobiphenyl 1 <0.5

2.2' ,4,4' -Tetrachlorobiphenyl 1 9.5 ± 0.4

2,2' ,4,4' ,5- Pentachlorobiphenyl 1 117 ± 5 2,2' , 4, 4' 5 , 5 ' -Hexachlorobiphenyl 1 127 ± 8 2,2'3,4,5,5' , 6 -Heptachlorobiphenvl 1 22.2 ± 1.0

2,2' ,3,3' ,4,4' ,5,5' -Octachlorobiphenyl 1 10.0 ± 0.4

2,2' ,3,3' ,4,4' ,5,5' , 6 -Nonachlorobiphenyl 1 18.2 ± 1.5

Hexachlorobenzene 1 <0.5

Heptachlor 1 <0.3

Aldrin 1 <0.5

o , p

' DDE 1 <0.5

p,p' DDE 1 1.9 ± 0.1

Mirex 1 <0.3

Lindane 2 <0.5

Heptachlor epoxide 2 0.6 ± 0.1

alpha- Chlordane 2 <0.2

Transnonachlor 2 0.9 ± 0.1

Dieldrin 2 <0.3

o , p

' DDT 2 1.4 ± 0.1

P,P' DDT 2 2.4 ± 0.1

aLC fraction 1 (PCB) is composed of the more nonpolar compounds

compared to fraction 2 (pesticide)

.

0Average of three extracts each analyzed 3 times.

cUncertainty is ±1 standard deviation of the mean.

32
552-36-009

1. Wise, S. A., Chesler, S. N. , Hertz, H. S., Hiipert, L. R. , and May, W. E., A

Chemically Bonded Aminosilane Stationary Phase for the High-Performance

Liquid Chromatographic Separation of Polynuclear Aromatic Compounds, Ar.al

.

Chem. 49 (14), 2306-2310 (1977).

2. Hertz, H. S., Brown, J. M. , Chesler, S. N. , Guenther, F. R. , Hiipert, L. R.

,

May, W. E., Parris, R. M. , and Wise, S. A., Determination of Individual

Organic Compounds in Shale Oil, Anal . Chem . 52 (11), 1650-1657 (1980).

3. May, W. E. , Chesler, S. N. , Hiipert, L. R. , Hertz, H. S., Rebbert, R. E.,

Vogt, C. R. , and Wise, S. A., Characterization of Polycyclic Aromatic

Hydrocarbons in Air Particulate Extracts by Liquid and Gas Chromatographic

Methods: Identification and Analysis of Organic Pollutants in Air, L. R.

Keith, ed. , Butterworth Publications, Woburn, MA, 197-229 (1984).

4. May, W. E. and Wise, S. A., Liquid Chromatographic Determination of

Polycyclic Aromatic Hydrocarbons in Air Particulate Extracts, Anal. Chem.

56, 225-232 (1984).

5. Wise, S. A., Chesler, S. N. , Hiipert, L. R. , May, W. E. , Rebbert, R. E., and

Vogt, C. R. , Characterization of Polycyclic Aromatic Hydrocarbon Mixtures

from Air Particulate Samples Using Liquid Chromatography, Gas

Chromatography, and Mass Spectrometry, Polynuclear Aromatic Hydrocarbons:

Mechanisms, Methods, and Metabolism, M. W. Cooke and A. J. Dennis, eds .

,

Battelle Press, Columbus, CH, 1413-1427 (1983).

6. Kline, W. F. , Wise, S. A., and May, W. E. , The Application of Perdeuterated

Polycyclic Aromatic Hydrocarbons (PAH) as Internal Standards for the Liquid

Chromatographic Determination of PAH in a Petroleum Crude Oil and Other

Complex Mixtures, J. Liquid Chromatogr. 1 (2), 223-237 (1985).

7. Parris, R. M. , Wise, S. A., and Chesler, S. N. , in preparation.

33

APPENDIX C

SRM CERTIFICATES

^Maiumal of jiitmriards

OJeriifkate of ^Attal^sts

Standard Reference Material 1583

Chlorinated Pesticides in 2, 2, 4-Trimethylpentane

ii E Derailment Commerce

’ Malcolnrfialdrige Secretary

'>V~ '

Nmoiul BureiaorSiandards

Emesl Ambler. Director

This Standard Reference Material (SRM) is intended primarily for calibrating methods used in the determination of the

chlorinated pesticides certified in this SRM. It can also be used for the purpose of adding known amounts of these

pesticides to a sample in recovery studies or to fortify samples with known concentrations of these pesticides. The

Chemical Abstracts Service (CAS) Nomenclature, common names, and CAS Registry Number of the six pesticide

components are listed in Table 1.

Certified Concentrations of the Pesticides: The certified concentrations and estimated uncertainties of the pesticides

are shown in Table 2.

Each value is based on the concentration calculated from the mass of the pesticide added to a known mass of 2,2,4-

trimethylpentane (isooctane) and on the analytical results obtained by using capillary gas chromatography with electron

capture detection (GC/ECD). The pesticides used were procured as being 99+ percent pure and GC and GC MS

analyses supported these claims. Table 3 shows the calculated concentrations and the concentrations obtained by the

analytical methods used in the certification. A noncertified concentration of heptachlor epoxide, which is given for information only, is also listed in Table 3.

NOTICE AND WARNING TO USERS

Handling: Pesticide-containing materials are reported to be toxic and should be handled with care. Proper disposal

methods should be used.

Expiration of Certification: This certification is valid within the specified uncertainty limits for one year from the date of

purchase. In the event that the certification should become invalid before then, purchasers will be notified by NBS.

Storage: Sealed ampoules, as received, should be stored in the dark at temperatures between 10 to 30 °C.

Use: Samples of the SRM for analysis should be withdrawn from ampoules (at 23 + 5

° C) immediately after opening and

used without delay for the certified values listed in Table 2 to be valid within the stated uncertainty. Certified values are

not applicable to material in ampoules stored after opening, even if they are rescaled.

Preparation and analytical determinations were performed at the Center for Analytical Chemistry, Organic Anal\ acal

Research Division, by S.N. Chesler, D.P. Enagonio, L.R. Hilpert, R.M. Parris, and C.R. Vogt.

Consultation on the statistical design of the experimental work and evaluation ot the data was provided by

K.R. Eberhardt of the Statistical Engineering Division.

The coordination of the technical measurements leading to the certification was under the direction of S.N. Chesler, W.E. May, and R.M. Parris.

The technical and support aspects involved in the preparation, certification, and issuance of this Standard Reterence

Material were coordinated through the Office of Standard Reference Materials by R. Alvarez.

Gaithersburg, MD 20899

February 11 , 1985

(over)

35

Stanley D. Rasberry. Chief

Office of Standard Reference Materials
PREPARATION AND ANALYSIS

Pesticides and 2,2,4-trimethylpentane were obtained from commercial sources. The pesticide solution was prepared at NBS by weighing and mixing the individual pesticides and 2,2,4-trimethylpentane. This solution was dispensed into

2-mL amber ampoules which were then flame sealed. Aliquots from randomly selected ampoules were analyzed with a gas chromatograph equipped with an injector splitter and a 30 m x 0.25 mm nonpolar, immobilized phase wall-coated

open-tubular column. A constant current Ni electron capture detector was used for these analyses. Quantitative

results were obtained by using 2,4',5-trichlorobiphenyi and 2,2',4,5,5 -pentachlorobiphenyl as internal standards

(IS). Calibration solutions consisting of weighted amounts of the pesticides and IS compounds in 2,2,4-trimethylpentane were chromatographed to determined analyte response factors.

Pesticide

7-BHC

Lindane

5-BHC

Aldrin

Heptachlor Epoxide

4,4'-DDE

p,p'-DDE

4,4 -DDT

p,p'-DDT

Table 1 Chemical Abstracts Service (CAS) Nomenclature and Registry Number*

CAS Nomenclature CAS Registry Number

(la,2a,3/?,4a,5a,6/?)-l,2,3,4,5,6-hexachlorocyclohexane 58-89-9

(la,2a,3a,4/3,5a,6/?)-l,2,3,4,5,6-hexachlorocyclohexane 319-86-8

( I or, 4a, 4a /3,5a, 8a, 8a/?)- 1 ,2,3,4, 1 0, 1 0-hexachloro- 1,4, 4a, 5, 8, 8a- 309-00-2

hexahydro- 1,4:5, 8-dimethanonaphthalene

2,3,4,5,6,7,7-heptachlor-la, lb,5,5a,6,6a-hexahydro-2,5-methano- 1024-57-3

2//-indeno( l,2-b]oxirene

I, l-(dichloroethenylidine)bis(4-chlorobenzene] 72-55-9

l,r-(2,2,2-trichloroethylidene)bis[4-chlorobenzene] 50-29-3

'Chemical Abstracts. Tenth Collective Index, Index Guide, American Chemical Society, Columbus, Ohio, 1982.

36
Table 2

Certified Concentrations of Pesticides in SRM 1583

Concentration*

5

Compounda Mg/g Mg/mLc

, 23 °C

7-BHC

5-BHC

Aldrin

p,p-DDE

p,p -DDT

1.11 ± 0.01 0.76 ±0.01

0.86 ±0.01

1.23 ±0.03

1.90 ±0.10

0.77 ± 0.01 0.53 ± 0.01 0.59 ± 0.01 0.85 ± 0.02

1.31 ± 0.07

*See Table 1 for CAS Nomenclature. For each compound, the certified value is the mean of the calculated and GC/ECD determinations. The corresponding

uncertainty represents the symmetrical interval about the certified value which encompasses the 95 percent confidence interval from the analyses that utilized gas chromatography with electron capture detection.

c The concentration and uncertainty expressed in mass/volume units are applicable for use of this material at 23 °C Since the density of 2,2.4-tnmethylpentane changes with temperature, the listed concentration will change by up to 1 percent of the value

listed if the SRM is used at other temperatures in the 14.6 °C to 31.4 °C range. See ‘‘Selected Values of Properties of Hydrocarbons and Related Compounds,” American Petroleum Institute Research Project 44, Thermodynamic Research Center, Texas A&M University, Table 3d, page 1, October 1952

Table 3 Summary of Results

Concentration, pg/g

Compound Calculated* GC/ECDb 7-BHC 1.1 12 ±0.001 1.109 ±0.010

5-BHC 0.768 ±0.001 0.761 ±0.007

Aldrin 0.861 ±0.001 0.861 ±0.010

p,p'-DDE 1.231 ±0.001 1.232 ±0.025

p,p'-DDT 1.900 ±0.002 1.899 ±0.100

Heptachlor Epoxide

0 — 0.997 ±0.016

‘Uncertainty expressed as ± 2o based on estimates of the precision of the weighings for the two balances used.

b Uncertainty expressed as 95 percent confidence interval.

e This value is for information only and is not certified.

37
U. S. Depanmeni of Commerce

Malcolm-Saldnge Secretary

—

National Surmu dFStandards

Ernest Amoter. Director ^uram nf Standards

dJsrtifirate of ^trains ts

Standard Reference Material 1585

Chlorinated Biphenyls in 2,2,4-Trimethylpentane (Isooctane)

This Standard Reference Material (SRM) is intended primarily for use in the calibration of chromatographic instru- mentation used for the determination of polychlorinated biphenyls. SRM 1585 consists of a set of five sealed ampouies

containing a solution of eight chlorinated biphenyl congeners in 2.2.4-tnmethvlpentane (isooctane).

CERTIFIED CONCENTRATIONS OF THE CHLORINATED BIPHENYL CONGENERS

The certified concentrations and estimated uncertainties of eight chlorinated biphenyl congeners are shown in Table I. Each value is based on the concentration calculated from the mass of the congener added to a known mass of L2.4-mmethylpentane and on the analytical results obtained by using capillary gas chromatography with electron capture

detection (GC-ECD). Calculations of the values included correction of the measured mass of each congener by its measured purity. The uncertainties listed in Table 1 include estimates of both purity and chromatographic uncertainty

components.

The calculated concentrations, the concentrations determined by the GC-ECD method, and the measured purities of the

compounds are given in Table 2. The certified concentrations in Table 1 were derived from these data. The concentrations given in Table 2 have been corrected for the purity of the congeners determined by capillary GC equipped with

flame ionization detection (GC-FID).

The significance of each of the chlorinated biphenyl compounds present in SRM 1585 is indicated in Table 5.

Expiration of Certification: This certification is valid within the specified limit of uncertainty for one year from the date

of purchase. In the event that the certification should become invalid before then, purchasers will be notified bv NBS

Storage: The sealed ampoules should be stored as received, in the dark, at temperatures between 10 to 30 5 C.

Use: Samples of the SRM for analysis should be withdrawn from ampoules immediately after opening and used without

delay for the certified values listed in Table 1 to be valid within the stated uncertainties. Certified vaiues are not applicable to material stored in ampoules after opening, even if the ampoules are resealed.

Preparation and analytical determinations were performed by S.N. Chesler, D.P. Enagomo, and R.M. Pams of the Organic Analytical Research Division, NBS Center for Analytical Chemistry.

Consultation on the statistical design of the experimental work and evaluation of data was provided by K. R. Eberhardt

of the NBS Statistical Engineering Division.

The coordination of the technical measurements leading to the certification was under the direction of S.N. Chesler and

R.M. Parris. The technical and support aspects involved in the preparation, certification, and issuance of this Standard Relerence

Material were coordinated through the Office of Standard Reference Materials by R. Alvarez.

January 30, 1986 Stanley D Rasberry, Chiet

Gaithersburg, MD 20899 Office of Standard Reference Materials

(over)

38
PREPARATION AND ANALYSIS

The chlorinated biphenyl compounds and 224-trimethylpentane were obtained from commercial sources. A solution was prepared at NBS by weighing and mixing the individual compounds and 2,2,4-trimethylpentane. This solution was

dispensed into 2-mL amber ampoules which were then flame sealed. Aliquots from randomly selected ampoules were

analyzed using a gas chromatograph equipped with an injector- splitter and a 30 m x 0.25 mm nonpolar, immobilized

phase, wall-coated, open-tubular column. A constant current

3J Ni electron capture detector was used for these analyses.

Quantitative results were obtained by -using 22’, 3,3’-tetrachloro biphenyl (C3 } 40) and 22\3,4,5,5’-hexachlorobiphenyl

(CB # 141) as internal standards (IS). Calibration solutions consisting of weighted amounts of the compounds and IS

compounds in 224-trimethyipentane were analyzed chromatographically to determine analyte response factors. The estimated purity of each chlorinated biphenyl component was determined using a gas chromatograph equipped

with a 30 m x 0.25 mm non-polar, immobilized phase, wall-coated, open-tubular column and a flame ionization detector.

Hexane solutions of each compound were analyzed and the relative response factors of the impurities were determined

using the method of Zoiler et al.

Reference

Zoiler, W., Schafer,

CB

W„ Class, T., and Ballschmiter, K., Fresenius Z. Anal. Chem. 321, 247-251 (1985).

Table 1

Certified Concentrations of Chlorinated Biphenyls in SRM 1585

Concentration

1 No. Compound Mg/g M?/mLc at 23.0'

3 4-chloro biphenyl 43.3 ± 1.0 29.9 ± 0.7

15 4,4’-dichiorobiphenyl 9.53 ±0.08 6.57 ± 0.06

28 24,4’-trichloro bip henyl 3.70 ±0.02 255 ± 0.01 52 22\5,5*-tetrachiorobiphenyl 7.72 ±0.06 5.32 ± 0.04

77 3,3’, 4, 4*-tetrachlo ro bip henyl 6.62 ±0.05 4.56 ± 0.03

101 2,2’, 4, 5,5*-pentachloro bip henyl 5.24 ±0.02 3.61 ± 0.01 138 2,2’,3,4,4\5’-hexachlorobiphenyi 237 ±0.02 1.63 ± 0.01 153 2,2*, 4, 4’, 5,5’-hexachlo robip henyl 3.06 ±0.02 211 ± 0.01 For each compound, the certified concentration is the mean of the calculated concentration and chromatographic determination. Both calculated and

experimental concentrations were corrected for the percent purity of the chlorinated biphenyl components.

The stated uncertainty was computed as a 95% confidence interval for the chromatographic measured value plus an allowance for systematic error. The

confidence interval reflects measurement error for both the purity of the CB congener components as well as the concentration measurements for the SR M itself The allowance for systematic error is the magnitude of the difference between the certified value and the chromatographic determination.

Ballschmiter, K.. and Zell, M., Fresemus Z.. Anal Chem. 302. 20-31 (19803. 'The concentration and uncertainty expressed in mass/volume units are apphcable for use of this material at 23.0 °C. Because the density of 2,2.4-tri- methylpcntane changes with temperature, the concentration will also change as temperature changes and will be different than the value at 23.0 °C

However, the concentrations will change by less than one percent of the value listed if the SR M is used at temperatures in the 15 to 3 1 °C range. See

“Selected Values of Properties of Hydrocarbons and Related Compounds.-* American Petroleum Institute Research Project 44. Thermodynamics

Research Center, Texas AdtM University, Table 3d, page 1, October 1952.

SRM 1585

Page 2

39
Table 2 Summary of Results

CB No.

- -Concentration

Calculated

5 \ Mg/g- - GC-HCDe Capillary GC-FID puntv,

weieht nercent

3 43.23 ±0.03 43.45 ±0.88 99.93 ± 0.02

15 9.544 ±0.011 9.518 ± 0.067

' 96.92 ± 0.09

28 3.696 ±0.003 3.703 ± 0.020 99.44 ± 0.02

52 7.714 ±0.010 7.720 ± 0.058 97.74 ± 0.04

77 6.629 ±0.009 6.606 ± 0.038 97.47 ± 0.17

101 5.234 ±0.004 5.244 ± 0.019 97.90 ± 0.09

138 1373 ±0.002 1362 ± 0.009 99.54 ± 0.01 153 3.060 ±0.003 3.054 ± 0.012 97.66 ± 0.02

'Concentrations are corrected for the purity of the compounds.

Uncertainty is expressed as ^ 2a based on estimates of the accuracy and precision of the weighings performed on

the rwo balances used. 'Uncertainty of the gas chromatographic (electron capture detection) results is ex Dressed as 95 percent confidence

limits.

dThe purity values shown here reflect the presence of only the impurities that had a flame loruxation detector (FID)

response during the capillary GC analysis. Uncertainty of the purity determinations is expressed as the standard

error.

C3 No.

3

15

28

52

77

101

138

153

Compounds in SRM 1585

Table 3

Significance of Chlorinated Biphenyl

Compound

4-chlorobiphenyl

4, 4’-dichioro biphenyl

2, 4, 4’- trichlo ro bi p heny1

12\5,5’-tetrachiorobiphenyi

3,3\ 4, 4’-tetrachloro biphenyl

2,2*, 4,5,5’-pentachio ro biphenyl

12%3,4,4’,5-hexachlorobiphenyl

2,2*, 4, 4\5,5’-hexachloro biphenyl

Significance

incidentally generated as a by-product of some industrial processes

incidentally generated as a by-product of some industrial processes

indicative of the presence of

Aroclors 1016. 1242

indicative of the presence of

Aroclors 1016. 1242

an especially toxic PCB compound

indicative of the presence of

Aroclors 1254. 1260

indicative of the presence of

Aroclors 1254, 1260

indicative of the presence of

Aroclors 1254. 1260

SRM 1585

Page 3

40
» .3

S. Deoartment of Commerce

Malcolm Bajdrige Secrexarv s- -

Manorial Bureau of Standards

Ernest Ambler. Director c

/Maiimtal IHurmu

tilzriiiizntz of

of Jiiandards

^naljjsis

Standard Reference Material 1586

isotopicaily Labeled and Unlabeied

Priority Pollutants in Methanol

This Standard Reference Material (SRM) is intended primarily for use in the evaluation and calibration of analytical

instrumentation used for the determination of priority pollutants as classified by the U.S. Environmental Protection

Agency (EPA). In particular this SRM may be used to calibrate and/or test a laboratory’s use of EPA Analytical

Methods 1624 and 1625 (as well as 624-625 and 524-525). These methods specifically require the use of combined gas chromatography/ mass spectrometry (GC/MS) and the use of isotopicaily labeled internal standards. SRM 1586 is composed of two separate solutions. The ten Priority Pollutants in one solution (SRM 1586-2) contain either deuterium

or carbon-13 while the other solution (SRM 1586-1) contains the same compounds with no isotopes except those

naturally occurring.

Certified Values of Constituent Organic Compounds: The certified values for the selected organic constituents are shown in Table 1. These certified values are based on results obtained from the gravimetric preparation of these solutions

and from the analytical values determined by gas chromatography. Table 2 summarizes the calculated and analytically

determined concentrations.

Notice and Warnings to User

Handling: Priority Pollutants are reported to be toxic and should be handled with care. Use proper disposal methods.

Expiration of Certification: This certification is valid, within the limits certified, for one year from the date of purchase

In the event that the certification should become invalid before then, purchasers will be notified by NBS.

Storage: Sealed ampoules, as received, should be stored in the dark at temperatures between 10-30 °C.

Use: Samples for analysis should be withdrawn immediately after opening ampoules and should be processed without

delay for the certified values in Table 1 to be valid within the stated uncertainty. Certified values are not applicable to material stored in ampoules that have been opened, even if they are resealed.

Preparation and analytical determinations were performed at the Center for Analytical Chemistry, Organic Analytical

Research Division, by F.R. Guenther, D.J. Pereles, R.E. Rebbert, M.J. Welch and E. White, V.

Consultation on the statistical design of the experimental work was provided by K.R. Eberhardt of the Statistical Engineering Division.

The coordination of the technical measurements leading to certification was under the direction of S.N. Chesler and

W.E.. May.

The technical and support aspects involved in the preparation, certification, and issuance of this Standard Reference

Material were coordinated through the Office of Standard Reference Materials by R. Alvarez.

October 16, 1984 ' Stanley D. Rasberry. Chief

Gaithersburg, MD 20899 Office of Standard Reference Materials

(over)

41
Preparation and Analysis

All chemicals used in the preparation of SRM 1586-1 and 1586-2 were obtained from commercial sources and were deemed the best available at the time. The chemical purities, as determined by gas chromatography, are listed in Table 3 and were used in the determination of the certified values. The isotopic purities of the compounds in SRM 1586-2 as determined by mass spectrometry at NBS are shown inTable 4. Both solutions were prepared at NBS by weighing and

mixing the ten individual compounds and the methanol solvent. Each solution was chilled and ampouled into 2 mL-amber glass ampoules. Each ampoule was purged with nitrogen immediately before adding the solution and

sealing. Aliquots from randomly selected ampoules were analyzed by gas chromatography with flame ionization

detection. A glass column (2 mx2 mml.D.), packed with 60/80 Carbopack B and coated with 1% SP-I000 was used for determination of carbon tetrachloride and benzene. The internal standard (IS) for this analysis was 1,2-dichloropropane. A fused silica column (30 m x 0.25 mm I.D. x 0.25 y.m film of bonded dimethyl polvsiloxane) was used with

splitless injection for the determination of the other eight components. For SRM 1586-1 (unlabeled), o-xylene was the IS

for chlorobenzene while 6-chloro-m-cresol was the IS for phenol, nitrobenzene, 2-nitrophenol. 2,4-dichlorophenol and

naphthalene, and benzo(k)fluoranthene was the IS for bis(2-ethylhexyl) phthalate and benzo(a)pyrene. For

SRM 1586-2 (labeled) the same three internal standards were used but in addition bis(2-ethylhexyl) adipate was used as the IS for the bis(2-ethylhexyl) phthalate.

TABLE 1

Certified Concentrations of Priority Pollutants in SRM 1586

Compounds Concentration ( ^g/ g)' SRM 1586-1 Carbon tetrachloride 128.5 ± 0.5 Benzene 101.1 ± 0.8 Chlorobenzene 133.0 ± 0.6 Phenol 117.0 ± 1.3 Nitrobenzene 126.0 ± 1.1 2-nitrophenol 103.6 ± 3.2 2,4-dichlorophenol 102.5 ± 0.6 Naphthalene 126.5 ± 1.2

Bis(2-ethylhexyl)phthalate 63.9 ± 1.7 Benzo(a)pyrene 49.2 ± 0.2

SRM 1586-2 (See Table 3 for isotopic purity of these compounds)

Carbon tetrachloride1

3

C 124.4 ± 2.1 Benzene-d6 99.0 ± 0.5 Chlorobenzene-ds 144.0 ± 1.3

* Phenol-ds 116.0 ± 0.6 Nitrobenzene-ds 134.5 ± 1.4

2-nitrophenol-d4 101.9 ± 2.3

2,4-dichlorophenoI-d3 82.2 ± 1.6 Naphihalene-ds 126.6 ± 1.0

Bis[2-ethylhexyl]phthalate-d4 60.4 ± 0.7 Benzo(a)pyrene-d 1

2

44.1 ±2.1

*For each compound, the certified value is the mean of the calculated and chromatographic determinations. The corresponding uncertainty represents the symmetric interval about the certified value which

covers the 95% confidence interval from the chromatographic analyses. Thus, the uncertainty rellecu both random error of measurement and the systematic bias between the calculated ind chromatographic values. -Weighed as phenol-d6, but in methanol solution it converts quantitatively to phenol-ds

SRM 1586

Page 2 42
TABLE 2 Summary of Results

Calculated Values, Analytical Values,

Compound Mg/ g Mg/ g

Priority Pollutants SRM 1586-1

Carbon tetrachloride 128.60 128.4 ± 0.4 Benzene 100.82 101.3 ± 0.6 Chlorobenzene 132.63 133.3 ± 0.3 Phenol 117.30 116.6 ± 1.0 Nitrobenzene 126.01 125.9 ± 1.0 2-nitrophenol 104.39 102.9 ± 2.5 2,4-dichlorophenol 102.42 102.6 ± 0.5 Naphthalene 126.74 126.3 ± 1.0 Bis[2-ethylhexyl]phthalate 64.16 63.6 ± 1.4 Benzo(a)pyrene 49.15 49.2 ± 0.2

Priority Pollutants SRM 1586-2

Carbon tetrachloride1

3

C 123.5 125.2 ± 1.3 Benzene-d6 98.7 99.2 ± 0.3 Chlorobenzene-ds 143.5 144.4 ± 0.9 •Phenol-ds 115.9 116.0 ± 0.6 Nitrobenzene-ds 134.0 135.0 ± 0.9 2-nitrophenol-d4 102.3 101.4 ± 1.8 2,4-dichlorophenol-d3 82.4 82.0 ± 1.4 Naphthalene-d8 126.5 126.7 ± 0.9

Bis[2-et hy1 hexyl]pht halate-dt 60.2 60.6 ± 0.5 Benzo<a)pyrene-d 1

2

43.8 44.4 ± 1.8

‘Uncertainties are given as 95% confidence intervals. 'Weighed as phenol-d*. but in methanol solution it converts quantitatively to phenol-d;.

SRM 1586

Page 3

43
TABLE 3 Chemical Purity of Priority Pollutants in SRM 1586

Determined by Gas Chromatography

Compound Purity %

SRM 1586-1 Carbon tetrachloride 99.9

Benzene 99.9

Chlorobenzene 99.9

Phenol 99.9

Nitrobenzene 99.9

2-nitrophenol 99.9

2.4-

dichlorophenol 99.9

Naphthalene 99.4

Bis[2-ethyihexvl]phthalate 99.5 Benzo(a)pyrene 99.5

SRM 1586-2

Carbon tetrachlorideI3 C 99.6

Benzene-ds 99.9

Chlorobenzene-d5 99.9

Phenol-d6 99.9

Nitrobenzene-ds 99.9

2-nitrophenol-d4 99.9

2.4-

dichlorophenol-d3 98.4

Naphthalene-d8 99.8 Bis[2-ethylhexyl]phthalate-d4 96.

7

Benzo(a)pyrene-di: 98.1

TABLE 4

Isotopic Purity of Priority Pollutants in SRM 1586-2

Determined by Mass Spectrometry

Compound

Carbon tetrachloride13 C

Benzene-d6

Chlorobenzene-ds

*Phenol-d6

Nitrobenzene-ds

2-nitrophenol-d4

2,4-dichlorophenol-d3

Naphthalene-d8

Bis[2-ethylhexyl]phthalate-d4

Benzo(a)pyrene-di2

Isotopic Purity. Percent

99.5 99.7

99.6

98.3 (as d;) 99.6

98.9

98.7

99.5 98.6 (aromatic ring only)

98.8 •Weighed as phenol-d« but in methanol solution it converts quantitatively 10 phenol-di.

Percent of Molecules

Totally Labeled

99.5

97.9

97.9

91.4 (as ds) 97.8

95.5 96.0

95.6

94.5 (aromatic nng only)

86.2

SRM 1586

Page 4

44
I s. Department of Commerce

Malcoinr&aldrige Secmaryr

National BurowtoTStandards

Ernest 'Am bter. Director

(SJgritfttair of

of jitaiutards

^nal^sis

Standard Reference Material 1814

Dioxin (2,3,7,8-TCDD in isooctane)

Standard Reference Material (SRM) 1614 consists of separate solutions of unlabeled and labeled 2,3,7.8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) in 2,2,4-trimethylpentane (isooctane). Three ampoules contain approximately 1.2 ml.

each of an isooctane solution of unlabeied 2,3,7,8-TCDD, and three ampoules contain approximately 1.2 mL each of an

isooctane solution of C-labeled 2,3,7,8-TCDD. This SRM is intended primarily for use in the evaluation of analytical

methods used in the determination of 2,3,7,8-TCDD. It can also be used to fortify samples with known amounts of

2,3,7,8-TCDD. The C-labeled 2,3,7,8-TCDD can be used as an internal standard in methods based on gas chromatography/ mass spectrometry (GC/MS).

Certified Concentrations of 2,3,7,8-TCDD

The certified concentrations and estimated uncertainties of the unlabeled and

13 C-labeied 2,3,7,8-TCDD solutions are

given in Table 1. The concentration values are certified in ng/ g units, but are also reported in ng/mL units for user convenience. The

lj C-labeled solution is certified for the total concentration of all isotopic forms of 2,3,7,8-TCDD.

The isotopic purity of the

1 J C-labeled material was determined to be 98.2 ± 0. 1 atom percent C by mass spectrometry.

The fully

‘ 3 C-labeled compound, 2,3,7, 8-TCDD-13 Ci 2 , accounts for 80.7 ± 0.5 percent of the 2,3,7,8-TCDD molecules

in the sample.

The certified values are the weighted averages of gravimetric values, based on the concentration calculated from the mass

of 2,3,7,8-TCDD added to a known mass of isooctane and on the analytical results obtained using capillary gas chromatography with electron capture detection (GC/ECD). The uncertainties are two standard deviations of the certified

values. These uncertainties include the gravimetric and GC measurement variability and any observed material

heterogeneity.

NOTICE AND WARNING TO USERS

Handling

The toxicity and/or carcinogenicity of 2,3,7,8-TCDD has not been precisely defined; however, this material should

be treated as a potential health hazard. Ampoules should be opened and the contents used only by persons trained in proper handling techniques. Techniques used in handling radioactive and infectious materials are applicable to 2,3,7,8-TCDD. Users in the United States should contact their regional offices of the U.S. Environmental Protection

Agency for information regarding proper disposal of these materials; in other countries, they should contact the

appropriate organization responsible for public health or environmental control.

Trimethylpentane (isooctane), used as a diluent in this SRM, is stable when stored in closed containers at room temperature. It will not undergo hazardous polymerization. However, it is highly flammable and should be kept away from

oxidizing agents.

Gaithersburg, MD 20899

July 8, 1985

(over)

Stanley D. Rasberry. Chief

Office of Standard Reference Materials
Preparation and Analysis

Samples of the unlabeled 2,3,7,8-TCDD and UC-2,3,7,8-TCDD used in the preparation of SRM 1614 were donated by

R. Mitchum, National Center for Toxicological Research, Jefferson AK. The unlabeled 2,3,7.8-TCDD was originally

obtained from ECO Control, Inc., Cambridge, MA; and the

13 C:labeled 2,3,7,8-TCDD from Midwest Research

Institute, Kansas City, MO. The purities of the labeled and unlabeled 2,3,7,8-TCDD used in the preparation of this SRM were determined at NBS using mass spectrometry, nuclear magnetic resonance spectrometry, and GC with flame

ionization detection. The purities were found to be greater than 95%.

Solutions of the unlabeled 2,3,7,8-TCDD and the ’"C-labeied 2,3,7,8-TCDD were prepared at NBS by weighing and

mixing the appropriate compound and isooctane. Each solution was dispensed into 2-mL amber ampoules which were

then flame sealed. Aliquots from randomly selected ampoules were analyzed with a gas chromatograph equipped for

split injection and a 30m x 0.25mm i.d. wall-coated open-tubular column with a 0.25 nm film of a non-polar, immobilized

phase. A constant current electron capture detector ( Ni) was used for these analyses. Quantitative results were

obtained through the use of 2,2',4,4',5,5-hexachlorobiphenyl as an internal standard. Calibration solutions consisting

of weighed amounts of the analyte and the internal standard compound in isooctane were analyzed chromatographically

to determine response factors. A trichlorodibenzo-p-dioxin impurity present in both solutions was quantified using GC/MS with electron impact

ionization, selected ion monitoring, and the method of standard additions. Standard additions of unlabeled 2.3,7-

trichlorodibenzo-p-dioxin were made to the unlabeled and

13 C-labeled 2,3,7,8-TCDD solutions, and although the retention time of the trichlorodibenzo-p-dioxin impurity was coincident with that of the 2,3,7-isomer, this was not

sufficient to positively identify which isomer was present. Concentrations of the trichlorodibenzo-p-dioxin in the SR M

solutions are provided, for information only, in Table 2.

Expiration of Certification

This certification is valid within the specified limit of uncertainty for one year from the date of purchase. In the event that the certification should become invalid before then, purchasers will be notified by NBS.

Storage

Sealed ampoules, as received, should be stored in the dark at temperatures between 10 and 30°C. It is recommended that these materials be stored in a secure area in a double-sealed container.

Use

Samples of the SRM should be withdrawn from ampoules (at 23 ± 8 °C) immediately after opening and used without

delay for the certified values listed in Table 1 to be valid within the stated uncertainties. Certified values are not applicable to material in ampoules stored after opening, even if they are resealed.

Preparation and analytical determinations were performed in the NBS Organic Analytical Research Division by

S. N. Chesler, B. Coxon, L.R. Hilpert, R.M. Parris, R.E. Rebbert, M.J. Welch, and E. White V.

Consultation on the statistical design of the experimental work and evaluation of the data was provided by R.C. Pauie

of the NBS National Measurement Laboratory.

The coordination of the technical measurements leading to the certification of SRM 1614 was under the direction of L.R. Hilpert, R.M. Parris, and W.E. May.

The technical and support aspects involved in the preparation, certification, and issuance of this SRM were coordinated

through the Office of Standard Reference Materials by T.E. Gills.

SRM 1614

Page 2 46
Table 1

Certified Concentrations of 2,3,7,8-TCDD

1 in SRM 1614

Concentration

15

Compound 2.3.7.8- ng/g ng/ ml/, 23 °C

TCDD 98.3 ±3.3 67.8 ± 2.3

2.3.7.

8-

TCDD-13 C

d 95.6±1.5 65.9 ± 1.0

*CAS Registry Numbers: 2J,7,8-TCDD12 Cu: 1746-01-6; 2,3,7,8-TCDD13 Ci:: 76523-40-5, Chemical Abstracts, Tenth Collective Index, Index Guide, American

Chemical Society, Columbus, Ohio, 1982.

bThe uncertainties given represent two standard deviations of the certified values. These

uncertainties include the gravimetric and GC/ECD 2,3,7,8-TCDD measurement

variability, the trichlorodibenzo-p-dioxin measurement variability, and, for the unlabeled 2J,7,8-TCDD, the observed sample heterogeneity.

c The concentration and uncertainty expressed in mass /volume units are applicable for use of this material at 23.0 a C. Since the density of 2,2,4-trimethylpentane changes

with temperature, the concentration will change at temperatures other than 23.0 9 C. The concentration will change by less than 1 percent of the value listed if the SRM is used at temperatures in the 15 to 31 °C range.

dThe concentrations given represent the total concentrations for all isotopic forms of

2.3.7.8-

TCDD in the solution. The fully

13 C-labeled 2,3,7,8-TCDD accounts for 80.7 ± 0.5 percent of the 2,3,7,8-TCDD molecules in the sample. This value is provided

for information only.

Solution

Table 2 Concentrations of Trichlorodibenzo-p-dioxin

Compound

in SRM 1614 —Concentration

1—

.nj&&. ng/mL, 23 °C

Unlabeled trichlorodibenzo-p-dioxinI2 Ct 2 (1.5)

Labeled ( 13 C) trichlorodibenzo-p-dioxin13 Ci 2 (3.9)

(

1 . 0) (2.7)

Values not certified; provided for information only.

Page 3 SRM 1614

47
S. Department of Commerce

Malcolm Baldrige Secretary

National Bureau orStandards

Ernest Ambler. Director ^

aitnttal of Standards

Certificate of ^nalusis

Standard Reference Material 1647

Priority Pollutant Polynuclear Aromatic Hydrocarbons (in Acetonitrile)

This Standard Reference Material is intended for calibrating chromatographic instrumentation used in the determination of the polynuclear aromatic hydrocarbons (PAH’s) certified in this SRM. It is also useful in recovery studies lor adding known accurate amounts of these PAH’s to a sample: and because of its miscibility with water, it can be used to

fortify aqueous samples with known concentrations of PAH’s.

Certified Concentrations of the PAH’s:

The certified concentrations of the 16 organic constituents in acetonitrile are shown in Table 1. Because the density oi acetonitrile changes with temperature, these concentrations are certified for the temperature range of 2 1 to 25 3 C. Except

for chrysene and dibenz[a.h]anthracene, each value is based on the concentration calculated from the mass of the P A H

added to a known volume of the acetonitrile, on the analytical results obtained by high performance liquid chromatography (HPLC), and for six compounds, also by gas chromatography (GC). The concentrations of chrysene and

dibenz[a.h]anthracene, which did not dissolve completely, were certified based on the concordant results of the two

independent methods, HPLC and GC, only. The calculated concentrations of the other 14 PAH’s were corrected lor compound purity determined by GC. Thirteen of the 16 compounds added were at least 97.5% pure while the remaining

three were at least 94% pure. Table 2 shows the calculated concentrations and the concentrations obtained by the analytical methods used in the certification.

NOTICE AND WARNINGS TO USER

Expiration of Certification: This certification is valid, within the limits certified, for one year from the date of purchase

In the event that the certification should become invalid before then, purchasers wiil be notified by \BS

Storage: Sealed ampoules, as received, should be stored in the dark at temperatures between 10-70 C

Use: Samples of the SRM for analysis should be withdrawn from ampoules held at 23 r 2

; C immediately alter opemne

and used without delay for any certified value in Table I to be valid within the stated uncertainty. Certified value: are not applicable to ampoules stored after opening, even if resealed.

Analytical determinations were performed at the Center for Analytical Chemistry, Organic Analytical Research

Division, by J.M. Brown-Thomas, F.R. Guenther. D.K.. Hancock, and W.E. May

Consultation on the statistical design of the experimental work was provided by K. R. Eberhardt ol the Statistical l ngineering Division.

The coordination of the technical measurements leading to certification were periormed under the uirecto o >i W.E. May and H.S. Hertz. The technical and support aspects involved in preparation, certification, and issuance ol this Standard Reicrcnce

Material were coordinated through the Office of Standard Reference Materials by R. Alvarez.

Washington. D.C. 20234 George A. Uriano. c hicl December 7, 1981 Office of Standard Reicrcnce Materia.

\

(over)

43
PREPARATION AND ANALYSIS

The acetonitrile solution of the 16 PAH’s was prepared at Serco, Inc., Roseville, Minn, and ampouled cold into 5-mL

amber glass ampoules. The ampoules were purged with nitrogen just prior to filling and sealed under nitrogen. Samples

representing early, middle, and final stages of ampouling were analyzed by HPLC. No significant differences in concentration of the 16 compounds were found.

Randomly selected ampoules were analyzed for ail 16 PAH’s by HPLC on a Vydac ODS (5 nm) column using an

acetonitrile-water mobile phase. Four external standard solutions were used to provide quantitative data. GC on a fused silica SE-54 capillary column was used to determine 8 of the 16 compounds. Two standard solutions were

used to obtain compound responses relative to 1-methylpyrene and ja-tetraphenyL, the internal standards.

Ultraviolet absorption data between 205 and 600 nm are supplied as an aid in identifying each compound certified in this SRM. Table 3 gives the apparent specific molar absorbance for several prominent peaks in each spectrum. “Specific

absorbance” is defined here as absorbance per unit pathlength and unit concentration. The term absorptivity was

avoided because it is ambiguously defined (See Mielenz, K.D., Anal. Chem. 48, 1093-1094 (1976)). The term

“apparent" is used because no corrections have been applied to the data for the effects of internal multiple reflections

within the cuvette. The apparent molar specific absorbances were not corrected for PAH purity. Table 4 gives the

apparent specific molar absorbances for each PAH at 254.0 nm. The apparent specific molar absorbance at 254.0 nm

should be used with caution. Because the absorbances measured at 254 nm do not correspond to peak maxima, very

small changes in wavelength may result in significant changes in the absorbance reading. The magnitude of this change is reflected in the last column of Table 4 which gives the percent change t» for a 1.0 nm shift away from 254.0 nm. It is important that the user check the calibration of his instrument at 254 nm.

Table 5 gives aqueous solubility values for 15 of the PAH’s present in this SRM. These data, which are provided for information only, give an indication of how much of SRM 1647 can be added to a known volume of water without

exceeding the aqueous solubilities of the PAH’s.

49
Table 1. Certified Concentrations of Polynuclear Aromatic Hydrocarbons

in SRM 1647 at 23 ± 2 °C

ComDound Concentration, ua, mL*

Naphthalene 22.5 ± 0.2 Acenaphthylene 19.1 ± .2 Acenaphthene 21.0 ± .4 Fluorene 4.92 r .10 Phenanthrene 5.06 £ .10 Anthracene 3.29 ± .10 Fluoranthene 10.1 ± .2 Pyrene 9.84 ± .10 Benz[a]anthracene 5.03 ± .10 Chrysene 4.68 ± .10 Benzo[b]fluoranthene 5.11 r .10 Benzo[k]nuoranthene 5.02 £ .10 Benzo[a]pyrene o II o

ir*

Benzo[ghi]perylene 4.01 r .10 Dibenz(a.h]anthracene 3.68 £ .10 Indeno[ l,2,3-cd]pyrene 4.06 r .10

•The estimated uncertainty given for each compound is based on judgment,

and represents an evaluation of the combined effects of method imprecision,

and possible systematic errors among methods.

Tabie 2. Summary of Results by the Analytical Methods Used in Certification

Concentration. Mg mL

Calculated HPLC GC

Naphthalene 22.5 214 ±0.5

J

Acenaphthylene 19.0 19.2 ± .5 Acenaphthene 20.8 21.2 ± .4 Fluorene 4.89 4.96 £ .18 Phenanthrene 5.00 5.12: .18 Anthracene 3.25 3.33 £ .10 Fluoranthene 9.99 10.3 £ .5 Pyrene 9.82 9.85 r .58 3enz(a]anthracene 4.99 5. 12 r .14 4.97 £ 0.06

-1

Chrysene^ 4.69 ± .15 4.68 £ .06 Benzo[b]fluoranthene 5.11 5.13 £ .21 5.09 £ 06

Benzo[k]fiuoranthene 5.00 5.06 £ .15 4.99 £ .10 Benzo[a]pyrene 5.28 5.32 £ .13 5.31 £ .19 Benzo[ghi] perylene 4.00 4.09 £ .30 3.99 £ .14 Dibenz[a.h]anthracene

h 3.73 £ .12 3.63 £ .07

I ndeno[ 1 .2.3-cd]pyrene 4.07 4. II £ .15 4 02 £ 06

'Uncertainty is given as 959c confidence limns lor the mean

' incomplete dissolution of compound.

50
Table 3 Apparent Specific Molar Absorbances at A max

Compound , nm

Apparent specific

•~.olar absorbance

«», L-mol -cm Relative t a Compound Amai . nm

Apparent specific

molar absorbance

ta. L-mol ' em Relative ta

Naphthalene 120.4 I 00T, Huuranrhcne 235.6 50.800 :ix/, 185.7 4.0 358.3

:

: 16 2X3.4

) 5.9 3410 • r 16 275.x 5.9 3210 12 266.2 5.5 jCB.6 7.0 25X.2* 4.0 2862 81

2XI.I 35 Aeenaphthene 127.0 S4. 100 ioo';; 275-5 45

320.7 la 271.4 24 3124 1.3 2M_5 24

306.4 3.x 2WL6 7X 300.6 4.8 2X9.2 7.6 Pyrene 24a i S3. 100 100^, 2X0.7 6.6 3X4 56

3IS.9 33 Acenaphthylene 229.0 5I.XOO i<xr; 3U5.4 1.3 .3.18.X 7.7 294.1 5.3 321.6 19 2712 hO

310.6 15 261.8 29 274.6 4.5 251.7 13 264.6 5.0

* 131.0 52

207.0* 15 Huorcne 260.7 18.800 IOO1 ’, 299.6 47 Bcn/ta) 2X7.0 93.000 100', 2920* 2X anthracene 384.3 l.l 2XX.4 32 374.8 0.8 27U.X* 71 357.8 5.2

26.3.4 100 341.0 7.4 219.9 XX 327.8 6.5 314.2 5.0 Anthracene 251.5 1X6.000 IOO', 299.7 X.4 375.9 4.0 2765 KU

356.9 4.2 266.7 43

339.x lx 256.1 4| 324.1 1.5 227.7 221.2 5.X 221.7 39

2 IX. 2 5.6

I’henant htene 250.7 63.500 lUUS Chrysene 267.1 1.34.000 IOO', 2917 21 >tt7 0.5

2X 1.2 16 .3198 273.9 20 ;«v4 9 2 244.1 77 294.3 V6

219.x 32 2X 1.0 21 1.3 51 257.6 55

24l_2 16 22U.6 24

‘Shoulder

! "These values arc lor information only and arc not certified.

I 51
Table 4. Apparent Specific Molar Absorbances at 254.0 nm

Compound

Apparent specific

molar absorbance

t a , Lmol cm

X |(f

'

% Relative _ ta. 254.0 nm

x 1Q0

Am^.\

% error in

ta lor

1 nm error

Naphthalene 3.1 3.2% 11%

Acenaphthene 1.2 1.4 18 Acenaphthylene 2.2 4.1 2 Fluorene 17 '88 i Anthracene 96 52 52

Phenanthrene 43 68 16 Fluoranthene 13 25 6

Pyrene 10 12 5 Benz(a]anthracene 33 36 3 Chrysene 52 39 15 Benzo[b]lluoranthene 43 96 4 Ben/.o[k]lluoranthene 28 48 15 Benzo[u]pyrene 42 72

Benzo[ghi]perylenc 16 27 0.7 Diben4a.h]anthracenc 11 7 6 lndeno[ 1,2,3-edjpyrene 38 53 *>0

The values in this table are for information only and are not certified.

Table 5. Aqueous Solubility Data for the Individual PAH Compounds

Present in SRM 1647

Compound

Naphthalene

Acenaphthylene

Acenaphthene

Fluorene

Phenanthrene

Anthracene

Fluoranthene

Pyrene

Benz(a]anthracene

Chrysene

Benzo(b]fluoranthene

Benzo[k]fluoranthene

Benzo(a]pyrcne

Benzo{ghi]perylene

Dibenz(a,h]anthracene

Indeno( 1.2,3-cdjpyrene

Aqueous Solubility at 25 °C,

(ng; mL)

(31700)*

(3930)**

(1685)

( 1000)

(45)

(206)

(132)

(9.4)

(

1 . 8 )

(1.5)

( 0. 8)

(

1 . 6)

(0.7)

(0.5)'

( 0. 2)

4 These values arc supplied lor inlormalion and are not certified. The) arc provided lor users who wish to add this acclonitrilc solution to water lor recovers studies. Note that Ku

solubilities arc lor individual PAH's and may change in an aqueous solution ol the

16 I’AH's.

h

L). Mac Kay and W. ijhiu. J. Chem. Eng. Data. 22. 4 < I V77».

* W. Davis. M. Krahl and Ci. Clowes. J. Am. Chem. Noe. na. IUR-14 iiwa^l

All other solubility values were determined at NBb using Dynamic Coupled Column Liquid

Chromatographic Technique. 52
s DrtiftinerK Commerce miconBrSaldrige SeeSpryf

5u?5»3rSundanlJ ^UmOfcr. Director ^aitmtal lurau of Jsdamiarsis

Ceritftrair

Standard Reference Material 1643b

Trace Elements in Water

This Standard Reference Material (SRM) is intended primarily for use in evaluating the accuracy of trace element

determinations in filtered and acidified fresh water and for calibrating instrumentation used in these determinations.

SRM 1643b consists of approximately 950 mL of water in a polyethylene bottle, which is sealed in an aluminized bag to maintain stability. SRM 1643b simulates the elemental composition of fresh water Nitric acid is present at a concentration of 0.5 moles per liter to stabilize the trace elements.

Concentrations of Constituent Elements: The concentrations of the trace elements that were determined are shown in Table 1. The certified values are based on results obtained either by reference methods of known accuracy or by two or more independent, reliable analytical methods. Noncertified values, which are given for information only, appear :n parentheses.

Notice and Warnings to Users:

Expiration of Certification: This certification is invalid two years after the shipping date.

Precautions: The bottle should be shaken before use because of possible water vapor condensation. To prevent possible

contamination of the SRM, do not insert pipets into the bottle. After use, the bottle should be capped tightly and placed

inside the aluminized bag, which should be folded and sealed with sealing tape. This safeguard will protect the SRM

from possible environmental contamination and long-term loss of water.

Elemental determinations of ng/g levels are limited by contamination. Apparatus should be scrupulously cleaned and

only the purest grade reagents employed. Sampling and manipulations, such as evaporations, should be done m a clean

environment, for example, a Class 100 clean hood.

The overall direction and coordination of the technical measurements leading to this certification were pertormed under

the direction of E. Gamer, Chief of the Inorganic Analytical Research Division.

The technical and support aspects involved in the preparation, certification, and issuance of this Standard Reference

Material were coordinated through the Office of Standard Reference Materials by R. Alvarez.

Washington, DC 20234 Stanley D. RasberTy. Chief

May 18, 1984 Office of Standard Reference Materials

(over)

55
(Table 1 ) Concentrations of Constituent Elements

Element

concentration.

ng/g Element

Concentration,

ng/g

Arsenic

! 5 (49)** t j3 . 4b Lead 23.7 ± 0.7 Barium '3 --b ’ 5 44 ±2 1 3 Manganese ' ’ 28 ±2

Beryllium

‘ ' "a 19 ±2 Molybdenum"3,

5

85 ± 3 Bismuth

1 (H) Nickel

-3-3 49 ± 3 Boron

"3 Cadmium"6-3 -5 (94) Selenium' 5 9.7 ± 0.5 20 ± 1 Silver

1-5 9.8 ± 0.8 Chromium46 18.6 ± 0.4 Strontium -3-5 227 ±6

Cobalt

1 -5 26 ± 1 Thallium

'6 8.0 + 0.2 Copper

3 ' 46 21.9 ± 0.4 Vanadium 46 45.2 ± 0.4

T 2a. -la. 5 Iron 99 ±8 2a.

5

Zinc 66 ±2

The estimated uncertainty ;s based on judgment and represents an evaJuanon of the combined effects of method imprecision and possible systematic errors among methods. To convert to nanograms per milliliter, multiply bvthedensitv of the SR M

The density at 23 °C is 1.017 grams per milliliter. •

Values in parentheses are not certified.

I. Atomic absorption spectrometry, electrothermal — Atomic emission spectrometry,

a. dc plasma

b. flame

3. Laser enhanced ionization flame spectrometry

4. Isotopic dilution mass spectrometry,

a. resonance ionization

b. thermal ionization

5. Neutron activation, instrumental Source and Preparation of Material: SRM 1643b was prepared at the U.S. Geological Survey. National Water Quaiitv

Laboratory. Arvada. Colorado, under the direction of V.J. Janzer of that laboratory and J. R. Moody of the NBS Center

ior Analytical Chemistry. Only high-purity reagents were used and the containers were acid-cleaned and sterilized before

use. In the preparation, a polyethylene cylindrical tank was filled with distilled water and sufficient nunc acid to make

the solution approximately 0.5 moles HNOj per liter. Solutions containing known amounts of calcium, sodium,

magnesium, potassium, and the elements to be determined were added to the acidified water solution with constant

stirring. After thoroughly mixing, the solution was filtered, sterilized, and then transferred to one-liter polvethviene

bottles. The approximate concentrations, in jig/rnL, of Ca, Na, Mg, and 1C are resoecnvely 35, 3. 15. and 3.

Analysts:

Center for Analytical Chemistry, National Bureau of Standards

1 . K. A. Brietic 10. J. R. Moody

2. T. A. Butler 11 . L. J. Powell

3. E. C. Deal 11 T. C. Rains

4. M. S. Epstein 13. T. A. Rush

5 J. D. Fassett 14. S. F. Stone

6. 1C. Fitzpatrick 15. G. C. Turk

7. H. M. Kingston 16. R. L. Watters, Jr. 8 . R. M. Lindstrom 17. R. Zeisler

9. L. A. Machlan

56
Standard

NBS

^5s

Reference JTR

Materials R U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Standard Reference Material 2121-2129

Spectrometric Standard Solutions

Spring 1985

The NBS Office of Standard Reference Materials has available aqueous spectrometric solution Standard Reference

Materials (SRM’s). They are intended for use in atomic absorption spectrometry, optical emission (plasma) spectrometry, spectrophotometry, or any other analytical technique that requires aqueous solutions for calibration.

These SRM’s, listed below, are prepared from NBS-SRM’s or well-characterized high-purity metals or salts using NBS

high-purity acids. Most solutions are prepared gravimetrically to contain 10.00 mg/mL of the selected metal in a 10 percent acid medium. For SRM 2121, the volume of each solution is 35 mL: for the other SRM’s the volume of each

solution is 50 mL.

SRM’s 2121 through 2126 are now available; the others are planned to be issued at two month intervals until the senes

has been completed. Each of the SRM’s consists of four single-element solutions, contained in individual bottles.

SRM Metals

2121 Cadmium. Lead, Silver, and Zinc

2122 Barium, Calcium, Magnesium, and Strontium

2123 Lithium, Potassium, Sodium, and Rubidium

2124 Cobalt, Copper, Iron, and Nickel

2125 Boron, Chromium, Manganese, and Molybdenum

2126 Antimony, Arsenic, Selenium, and Tin

2127 Aluminum, Beryllium, Phosphorus, and Silicon

2128 Gold, Mercury, Palladium, and Platinum

2129 Titanium, Tungsten, Vanadium, and Zirconium

The first six of these SRM’s are now available for SI 60 per unit from:

Office of Standard Reference Materials

Room B311, Chemistry Building

National Bureau of Standards

Gaithersburg, MD 20899

Telephone: 301-921-2045

0485 57
U. S. Department of Commerce

Malcolm Baldrige 5ecmary7

' r

National Burmin of Standard!

Ernest Ambter. lSrector

This Standard Reference Material is intended primarily for calibrating instrumentation and evaluating the reliability of analytical methods for the determination of major, minor, and trace elements in sediments, and similar matrices

Values of Constituent Elements: The certified values for the constituent elements are shown in Table 1. They are based on results obtained either by definitive methods or by two or more independent, reliable analytical methods. Voncertified values, which are given for information only, appear in Table 2. All values are based on a minimum sample size of 500 mg of the material dried as indicated under “Instructions for Drying".

Notice to Users:

Expiration of Certification: The certification of this SRM will be invalid 5 years after date of shipping.

Use: The material should be kept in its original bottle and shaken well before each use. A minimum sample of 500 mg ol the dried material (see Instructions for Drying) should be used for any analytical determination to be related to a certified value of this certificate.

Statistical consultation was provided by K. R. Eberhardt of the Statistical Engineering Division.

The overall direction and coordination of the technical measurements leading to certification were performed in the Inorganic Analytical Research Division, E. L. Garner, Chief.

The technical and support aspects involved in the preparation, certification, and issuance of this Standard Rclcrencc

Material were coordinated through the Office of Standard Reference Materials by R. Alvarez.

Washington, D.C. 20234 George A. Uriano. Chic!

June 7. 1982 Office of Standard Rclcrencc Materials

(Revision of Certificate (over)

Standard Reference Material 1646

Estuarine Sediment

dated 1-6-82)

58
Table 1. Certified Concentration of Constituent Elements

Concentration, Concentration,

Element weight % Element weight %

Aluminum'b ’ L ’ 6 6.25 ± 0.20

1 c • 2c Magnesium • 1.09 ± 0.08

Calcium**’’*’

6 0.83 ± 0.03 Phosphorus'* 16 0.054 ± 0.005

, 2c;4ii;h Iron 3.35 ± 0.10

Concentration, Concentration,

Element Mg/g Element Mi, S

. . Id;4b Arsenic 11.6 ± 1.3

1 c * 2c Manganese ’ 375 ± 20 — , ib ta .b;;4b Cadmium 0.36 ± 0.07

.. la-4b Mercury ’ 0.063 ± 0.012

lc.lb.4a Chromium • 76 ±3 XI . . ,1b* 2c -

5

Nickel ’ ' 32 ± 3

Cobalt"’’"'"

1 10.5 ± 1.3 Vanadium**1 ''1,1 94 ± 1 - u ; :c4h

Copper ’ ' 18 ±3 _. Ib,c-2c-3b"5

Zinc ’ ’ ’ 138 ± 6

. . Ib-la- 5 Lead ' ’ 28.2 ± 1.8

1. Atomic absorption spectrometry 3. Isotope dilution mass spectrometry

a. cold vapor a. thermal ionization

b. graphite furnace b. spark source

c. flame 4. Neutron activation

d. hydride generation a. instrumental

2. Atomic emission spectrometry b. radiochemical

a. dc plasma 5. Polarography

b. flame 6. X-ray fluorescence spectrometry

c. inductively coupled plasma

Notes: ( 1.) Analytical values are based on the "dry-weight" of material (see Instructions for Drying). Mercury should be

| determined on samples without drying and the results adjusted to a “dry-weight" basis by determining the moisture

content of separate samples.

] (2.) The estimated uncertainty for an element is based on judgment and represents an evaluation of the combined effects of method imprecision, possible systematic errors among methods, and material variability for samples 500 mg or more.

59
Table 2. Non-certificd Concentrations of Constituent Elements

Note: The values shown in this table are not certified because they are not based on the results of either a definitive method or two or more independent analytical methods. These values are included, for information only, to provide

additional information on the composition.

Element

Concentration.

Weight % Element

Concentration.

Weight %

Potassium (1.4) Sulfur (0.96)

Silicon (31) Titanium (0.51)

Sodium (2.0)

Element

Concentration,

Mg/g Element

Concentration,

Mg/g

Antimony (0.4) Molybdenum (2.0)

Beryllium (1.5) Rubidium (87)

Cerium (80) Scandium ( 10. S) Cesium (3.7) Selenium (0.6)

Europium (1.5) Tellurium (0.5)

Germanium (1.4) Thallium (0.5) Lithium (49) Thorium (10)

Analysts:

inorganic Analytical Research Division, National Bureau of Standards. 1. L. Barnes, M. B. Blackburn, C. G. Blundell. T. A. Butler, M. S. Epstein, T. E. Gills, J. W. Gramiich, R. R. Greenberg, S. Hanamura, W. R. Kelly, H. M. Kingston.

L. Macnlan, E. J. Maienthal, J. D. Messman, T. J. Murphy, T. C. Rams, T. A. Rush, R. Sedivy, and R. L. Watters. Jr.

Cooperating Analysts:

University of Tokyo, Tokyo, Japan; present address: Meteorological Research Institute; Tsukuba, Ibaraki. Japan;

Y. Dokiya (NBS Guest Worker).

Division of Chemistry, National Research Council of Canada, Ottawa. Canada; S. Berman. A. Desaulniers, R. Sturgeon, A. Mykytuik. J. McLaren, V. Boyko, and P. Sememuk.

Instructions for Drying: Except for mercury, elements should be determined on samples that have been dried at 1 1 0 °

C

for 2 hours.

Mercury should be determined on undried samples. However, because the certified concentration is reported on a “dryweight' basis, the concentration determined on undried samples should be adjusted for the moisture content of the samples.

Source and Preparation of Material: The material for this SRM was supplied by R. Huggett. Virginia Institute of Marine Sciences, Gloucester Point, Va. It had been dredged from the Chesapeake Bay at a location: 37° II I 'N.

76° !7. l'W. The material was freeze-dried at Eastern Freeze-Dry Corporation, Lancaster. Pa., and radiation sterilized

at Neutron Products Inc., Dickerson, Md. At NBS. the sediment was sieved througn a screen with openings of 1.00 mm

(No. lb) to remove coarse contaminants; ball-milled to pass a sieve with openings of 150 Mm (No. 100); thorougnlv mixed

in a V-blender; placed in polyethylene bags; and bottled.

Homogeneity Assessment: A preliminary evaluation of homogeneity was made by instrumental neutron activation

using samples of approximately 250 mg taken from various locations of the bulk materials. The samples were irradiated

and the activities from radionuclides of Ce, Co, Cr, Cs, Eu. Fe, Rb, Sc and Th were counted. Except for Ce and Th. the observed sample-to-sample variations for the elements were approximately the same as the counting statistics indicating

satisfactory homogeneity for these elements within approximately 2%. The homogeneity of the material lor As. CJ. H g. N, and Zn was evaluated by various analytical techniques using samples weighting 250 to 300 mg and found to satisfactory. The homogeneity of the remaining certined elements was determined using sample weights not exceed

r. g one gram.

The uncertainties of the elemental concentrations in Table I take into account possible material mhomogene t'. >. samples weighing 500 mg.

60
APPENDIX D

NOAA/NBS Methods Development/Quality Assurance Workshop

Attendees

Dr, Elliot Atlas

Dept, of Oceanography

Texas A&M University

College Station, TX 77843

(409/845-2986)

Dr. Robert Barrick

Sr. Chemist

Tetra Tech

11820 NE Northup Way

Suite 100

Bellevue, WA 98005

(206/822-9596)

Mr. Donald Becker

React B108

National Bureau of Standards

Gaithersburg, MD 20899

(301/921-2166)

Dr. Shier S. Berman

Division of Chemistry

National Research Council

Ottawa KlA 0R6

CANADA

(613/993-2830)

Dr. John A. Calder

NOAA/NOS/OOMA

N/OMA32

Rockville, MD 20852

(301/443-8655)

Dr. Stephen Chesler

222/A113

National Bureau of Standards

Gaithersburg, MD 20899

(301/921-2153)

Dr. Robert C. Clark, Jr.

NOAA/NMFS F/NWC6

2725 Montlake Boulevard East

Seattle, WA 98112

(206/442-5596)

Dr. Adriana Cantillo

NOAA/NOS /OOMA

N/OMA32

Rockville, MD 20852

(301/443-8655)

61
Dr. Eric Crecelius (206/683-4151)

Battelle Northwest

439 West Sequim Bay Road

Sequim, WA 98382

Dr. Robert Eganhouse (617/929-8473)

Environmental Science Program

University of Massachusetts

Boston, MA 02125

Dr. Michael Epstein (301/921-2142)

222/B222

National 3ureau of Standards

Gaithersburg, MD 20899

Dr. S. Y. Feng (203/446-1020 ext. 273)

University of Connecticut

Marine Sciences Institute

Avery Point

Groton, CT 06340

Dr. Donald Gadbois (617/281-3600 ext. 286)

NOAA/NMFS F/NEC6/Gloucester Laboratory

Emerson Avenue

Gloucester, MA 01930

Mr. Richard Gossett (213/435-7071)

SCCWRP

'

646 W. Pacific Coast Highway

Long Beach, CA 90806

Joseph N. Hall II

EPA

Office of Marine and Estuarine Protection (WH-556M)

401 M St.

,

SW

Washington, DC 20460

Dr. Peter Hanson (919/728-3595)

NOAA/NMFS

Beaufort Laboratory

Beaufort, NC 28516

Dr. Charles 3. Henry (504/388-8521)

Institute for Environmental Studies

RM #32, Atkinson Hall

Louisiana State University

Baton Rouge, LA 70803

Dr. Harry S. Hertz (301/921-2851)

222/A309

National Bureau of Standards

Gaithersburg, MD 20899

62
Dr. David Kalman (206/543-4252)

School of Public Health

and Community Medicine

University of Washington

Seattle, WA 98195

Mr. Gunnar Lauenstein (301/443-8655)

N0AA/N0S/00MA

N/OMA32

Rockville, MD 20852

Dr. William MacLeod (206/442-4240)

NOAA/NMFS F/NWC6

2725 Montlake Boulevard, East

Seattle, WA 98112

Dr. Willie E. May (301/921-3773)

222/A113

National Bureau of Standards

Gaithersburg, MD 20899

Ms. Reenie Parris (301/921-2153)

222/A113

National Bureau of Standards

Gaithersburg, MD 20899

Dr. Robert Paule (301/921-2305)

223/A361

National Bureau of Standards

Gaithersburg, MD 20899

Dr. James R. Payne (619/456-7490)

Science Applications International

476 Prospect Street

La Jolla, CA 92037

Dr. Donald Phelps (401/789-1071)

Environmental Research Laboratory

USEPA

South Ferry Road

Narragansett , RI 02882

Dr. Richard H. Pierce

Mote Marine Laboratory

1600 City Island Park

Sarasota, FL 33577

Dr. Bob J. Presley (409/845-5136)

Department of Oceanography

Texas A&M University

College Station, TX 77843

63
Mr. Ted Rains (301/921-2142)

222/B222

Nacional Bureau of Standards

Gaithersburg, MD 20899

Dr. Stanley D. Rice

NOAA/NMFS/NWAFC

Box 155

Auke Bay, AK 99821

Dr. James Sanders

Director

Benedict Estaurine Research Laboratory

Benedict, MD 20612

Dr. Michelle (Miller) Schantz (301/921-2153)

222/A113

National Bureau of Standards

Gaithersburg, MD 20899

Dr. Robert Shokes (619/456-7506)

Science Applications International Corp.

476 Prospect Street

LaJolla, CA 92038

Dr. Jeff Short (907/789-7231)

NOAA/NMFS /NWAFC

Box 155

Auke Bay, AK 99821

Dr. Robert B. Spies (415/422-5792)

Lawrence Livermore National Laboratory

P.0. Box 5507 , L-453

Livermore, CA 94550

William G. Steinhauer (617/934-5682)

Battelle New England Marine Laboratory

397 Washington Street

Duxbury, MA 02332

Dr. John Taylor (301/921-3497)

222/A309

National Bureau of Standards

Gaithersburg, MD 20899

Dr. Terry Wade (409/845-3872)

Department of Oceanography

Texas A&M University

College Station, TX 77843

64
Dr. John Wells

NOAA/NMFS F/SEC3

P.0. Box 12607

Charleston, SC 29412

(303/762-1200 Comm)

(677-4773 FTS)

Dr. Stephen A. Wise

222/A113

National Bureau of Standards

Gaithersburg, MD 20899

(301/921-2154)

Dr . David Young (301/443-8655)

NOAA/NOS/OOMA

N/OMA32

Rockville, MD 20852

Mr. Vincent S. Zdanowicz

NOAA/NMFS F/NEC4

Sandy Hook Laboratory

Highlands, NJ 07732^

Dr. Rolf Ziesler (301/921-2166)

React B108

National Bureau of Standards

Gaithersburg, MD 20899

65
NBS-114A (rev. 2-ac) U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET (See instructions

)

4. TITLE AND SUBTITLE

. PUBLICATION OR 2 REPORT NO.

. Performing Organ. Report NoJ 3. Publication Date

Summary Report of NOAA-NBS Quality Assurance Workshop

5. AUTHOR(S)

6. PERFORMING ORGANIZATION (if joint or other than NBS, see instructions) 7. Contract/Grant No. NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

NA86 AANCG0074

8. Type of Report & Period Covered

FINAL, FY86

3. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. State, ZIP)

National Oceanic and Atmospheric Administration

National Ocean Service

Office of Oceanography and Marine Assessment

Rockville, MD 20852

10.

SUPPLEMENTARY NOTES

('" 1 Document describes a computer program; SF-185, FlPS Software Summary, is attached.

11.

ABSTRACT (A 200-word or less factual summary of most significant in formation. If document induces a significant

bibliography or literature survey, mention it here)

This report suumarizes the proceedings of a methods development, quality

assurance workshop held at the National Bureau of Standards, December 5-6, 1985, as part of NOAA's continuing effort to improve the quality of marine monitoring

data. The workshop consisted of a series of contributed papers and group

discussions of the results of collaborative measurements of a group of test

samples. Summaries of the papers and the group discussions are included in

this report.

12.

KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key woras ov semicolon s i Analytical chemistry; collaborative tests; data quality; marine monitoring data;

methods development; quality assurance

13. AVAILABILITY 14. NO. OF

PRINTED PAGES

| j Unlimited

| y- 1 For Official Distribution. Do Not Release to NTIS

i

I Order From Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402.

66

IS. Price

i Order From National Technical Information Service (NTIS), Springfield, VA. 22161 $11.95

uSCOmm*OC • O 4 1 • 0