NBS/EPA Energy Environment Project

SEMI-ANNUAL REPORT

TO

ENVIRONMENTAL PROTECTION AGENCY

OFFICE OF ENERGY, MINERALS, AND INDUSTRY

WASHINGTON, D.C. 20460

.

A111DQ

July - December 1979

Issued May 1980

EPA-IAG-D8-E684

. U56

80-2048

1980

c,2

NBSIR 80-2048

U.S. Department of Commerce

National Bureau of Standards

Washington, D.C. 20234
IIIIIIIIII
AYIONAL BUREAU

OV STANDARDS

LIBRARY

TABLE OF CONTENTS

FOREWORD

LIST OF TABLES

LIST OF FIGURES

INTRODUCTION AND SUMMARY

80 -BCKa -ENERGY RELATED POLLUTANT MEASUREMENT AND

INSTRUMENTATION AND DEVELOPMENT

1 Energy-Related Water Pollutant Analysis

Instrumentation

l.a Development of Marker Compounds

1 . b Application of Selective Detectors to Liquid

Cnromatography^ ! ! ! ^ ^ ^ ] ! . ] . .

l.c Liquid Chromatography-Mass Spectrometry . . . .

1 . d Feasibility Study of Application of Particulate

Analysis by Ion Microprobe" i ] !! i ^ i ^ T .

1 . e Liquid Chromatograph with Electrochemical

Detection of Organometallic Compounds . T . . . l.f Laser Enhanced Ionization

1 . g Speciation of Inorganic Pollutants

SEP 1 9 1980

f)0i cut- tore*

Page

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80 -BCKb -ENERGY RELATED WATER POLLUTANT ANALYSIS

INSTRUMENTATION

1 Development of Measurement Methods for Non-Volatile

Organic Pollutants in Water Due to Energy

Technologies . ^ ^ ^ ^ i i ! T 12

1 . a Raman Microprobe Characterization of Trace

Polynuclear Aromatic Hydrocarbons i ^ ! ] 12

1 .b Development of Specific Immunoassays for

Dini trophenol s in Water . ! i [ ! ! ^ ] 13
80 -BCLa- ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 D evelopment of SRM's for Stationary Sources

Associated with Energy Production 15

l.a NC>

2

in Air Gas Blend SRM's ^5

l.b S0

2

in N

2 SRM 16

l.c NO in N

2

SRM

.

. 16

l.d 0

2

in N

2

SRM's

1.

e Stationary Source Gas SRM's 16

2 Development of SRM's for the Monitoring of Ambient

Air Impacted by Emissions Resulting from Energy

Production 16

2.

a Trace Level Reactive Gas SRM's 16

2.b C0

2

in Air *

2.c Automation of Gas Analysis 17

2

.

d Development of a Traceability Procedure for Gas

Standards . ! [ ! ! i ! ! 1! . i ] ] I ^ i I i T ... 17

3 Develop Methods for Dispersal of Particulates on

Filter Media and Methods for Determining and

Controlling the Composition and Morphology of

Such Dispersed Particulates . ] ! . . ] 7 . T .... 18

3

.

a Thin Glass Films Produced by Focused-ion Beam

Sputtering 18

4 Particulate Physical and Chemical Characterization . . 19

4.

a Particle Doppler Shif.t Spectrometer (PDSS) 19

5 Particulates on Glass Fiber Filters 20

5

.

a \ Certification of SRM's for Pb , Sulfate, and Nitrate

on Filter Media 20

6 Urban Air Particulate Washington D. C. Sample .... 25

7 Develop SRM's for Coal Conversion Processes and

Materials Balance Determinations 25

8 Development of an Oil Shale SRM 26
80-BCLb-ENERGY RELATED AIR POLLUTANT ANALYSIS INSTRUMENTATION

1 Development of an Instrument to Measure Airborne

Sulfate Particulate Matter^ ] !! ] ] i ! ! i i ... 27

80 -BCLc-ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 Radiocarbon as an Environmental Tracer 29

l.a Applications 29

l.b Research Advances 3]

2 Organics on Air Particulates 33

80 -BCMa-ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 Energy Related Water Pollutant Standard Reference

Materials 41

l.a Complete Certification of Ocean Sediment SRM 41

1 . b Complete Certification of SRM 1646, Estuarine

Sediment^ ^ ! ! ] ! ! ] ] ! ^ ^ ^ ^ ^ ! T .... 41

l.c Trace Elements in Water, SRM 1643 41

l.d Aqueous Polynuclear Aromatic Hydrocarbon Standard

SRM 1644 . . . . . . . . . . . . . 41

2 Matrix Isolated Laser Raman Identification of GC

Effluents . ] ! ’

] [ ] ! ! i ! i ! ! ] ] [ ! ] . . . 42

80 -BCMb- ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 Develop Organic SRM's for the Calibration of Energy - Related Water Pollutant Measurement Methods . ’

i 7 . 4

5

l.a Coal Conversion 45

1 • b Analysis of Phenolic Species in Alternate Fuels

and Effluents ! ! ! ] . . i i i i [ 1! ] ] ^ ^ T ... 45
l.c Development of a Phenol in Water SRM

1 . d Inter laboratory Compar i s on

80-BCN-ENERGY RELATED POLLUTANTS AND EFFECT MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 Radio logi cal Pollutant Quality Assurance

1 . a Solution of Plutonium- 241

1 . b Fly Ash from Coal Combustion Assayed for Radium- 226

and Radium- 22 8 ! ! i I I i ! . l.c Thorium-232 'Solu11 on

l.d Mixed Radionuclide Solutions

2 Measurement Traceability Studies with Analytical

Quality Control of EPA-LV. [ i

~

i i ] .. ’ 7
FOREWORD

The role of the National Bureau of Standards (NBS) in the

Interagency Energy/Environment R§D program, coordinated by the

Office of Research and Development, U. S. Environmental Protection Agency, is to provide those services necessary to assure

data quality in measurements being made by a wide variety of

Federal, state, local, and private industry participants in the

entire program. The work at NBS is under the direction of the

Office of Environmental Measurements and is conducted in the

Center for Analytical Chemistry and the Center for Radiation

Research. NBS activities are in the Characterization, Measurement, and Monitoring Program category and address data quality

assurance needs in the areas of air and water measurement

methods, standards, and instrumentation. NBS outputs in support

of this program consist of the development and description of

new or improved methods of measurement, studies of the feasibility of production of Standard Reference Materials for the

calibration of both field and laboratory instruments, and the

development of data on the physical and chemical properties of

materials of environmental importance in energy production.

This report is one of a series issued every six months by NBS to

provide information to the Interagency Energy/Environment

community on the status of methods, standards and data projects

at NBS. Detailed project information is also provided in the

Interagency Energy/Environment Research and Development Series.

C. C. Gravatt

Chief, Office of Environmental Measurements

National Bureau of Standards

LIST OF TABLES

page

Table 1--Current Studies of the Chemical and Isotopic

Purity Checks 2

Table 2 - -Concentrator Flow Rates 3

Table 3 -- Intercomparisons of N0 ? in Air Cylinders for

Certification 13

Table 4--Nominal Composition of Proposed Glass Targets

(A-C) for 1980 IB

Table 5--Recovery of Potentially Available Response vs.

Precipitator Frequency 28

Table 6--PAHs Identified in Urban Air Particulate Matter

(SRM 1648) a 38

Table 7--Phenol and O-cresol Concentrations in Shale Oil. . 46

Table 8--Phenol Concentrations 50

Table 9--Reference Samples with Known, but Undisclosed,

Values Provided to EPA-LV by NBS 53

iii
LIST OF FIGURES

page

Figure 1-- UV and MS chromatograms from direct HPLC

injection of 1 microliter of shale oil

containing 400 ppm of phenol 5

Figure 2-- Generator-Detector (G-D) thin layer cell 8

Figure 3-- Comparison of G-D cell response to that of a single electrode cell 9

Figure 4 -- Detection of organotin cations with G-D cell. . . 10

Figure 5-- Percent of contemporary (biogenic) carbon

deduced from radiocarbon measurements on

small 10 mg) environmental samples 30

Figure 6-- Wood as a fuel: utilization and particulate

pollution 32

Figure 7-- Magnification of age uncertainty interval of a dated wood sample because of natural radiocarbon

variations 34

Figure 8-- Normal phase liquid chromatogram of PAH extracted

from urban air particulates 35

Figure 9-- Gas chromatograms of fractions 3, 4, and 5. . . . 36

Figure 10- -Reserve phase liquid chromatographic analysis

of fraction 4 from urban air particulates .... 40

Figure 11- -Acid extract of shale oil chromatographed on

20 m PL-64 column 47

IV
page

Figure 12--SIM analysis of HPLC fractionated shale oil. . . 48

Figure 13--Standard addition quantitation of o-cresol in

shale oil 49

v
INTRODUCTION AND SUMMARY

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This report describes work performed by the National Bureau of

Standards (NBS) during the period, July 1979 to December 1979,

under the Interagency Agreement (EPA- IAG-D8 -E684) between the U.S.

Environmental Protection Agency and NBS. This Agreement covers

the development of standards, methods, data, and instrumentation

for quality assurance of measurements of pollutants associated

with energy production and use. The highlights for this reporting

period in the eight sub-agreement areas are given below.

80 BCKa - ENERGY RELATED POLLUTANT MEASUREMENT AND INSTRUMENTATION

DEVELOPMENT

Under the task, " Energy Related Water Pollutant Analysis Instru - mentation" , a revised list of 23 marker compounds to be used in

the Master Analytical Scheme were received. NBS has obtained,

synthesized, and performed chemical and isotopic purity checks on

most of the compounds. The chemical purity of the compounds was

checked by gas chromatography or liquid chromatography and mass

spectrometry. The isotopic purity of the compounds was also

checked by mass spectrometry. All of the compounds tested thus

far appear to be of satisfactory chemical and isotopic purity for

their intended purpose, except for 1 , 2-dichloroethane-d^

.

Additional refinements have been incorporated into the liquid

chromatography-mass spectrometry system (LC-MS) : installation

and calibration of a sensor, changes to optimize configuration

location, and replacement of one of the vacuum flanges with a viewport and telescope to permit viewing the operation of the

LC-MS interface probe in situ . The system has been applied to

analytical problems and encouraging results were obtained.

Patent application for the interface has been filed by EPA.

vi
Work related to the measurement of trace organometallics using

liquid chromatography- electrochemical detection (LC-EC) has focused

on the development of electrochemical detectors. A new detector

has been developed that enables measurements to be performed in a normal laboratory environment without sacrificing detection limits.

In addition, an Interagency Energy/Environment Research and

Development Program Report describing activities with the LC-EC

technique was issued this reporting period (EPA- 600/ 7 - 79 - 211)

.

Preliminary experiments with metal specific detectors and high

performance liquid chromatography (HPLC) has shown some promise as

an analytical technique for speciation of inorganic pollutants.

Work is continuing on the development of methods using such an

approach to identify and measure inorganic species in effluents.

80 BCKb - ENERGY RELATED WATER POLLUTANT ANALYSIS INSTRUMENTATION

Under the task, " Development of Measurement Methods for Non - Volatile Pollutants in Water due to Energy Technologies , experiments have been performed using the Raman microprobe technique to

optimize the isolation of trace fractions in effluents, and to

identify and measure components of the effluent.

Most of the reagents for labeling antibodies required for work on

the development of specific immunoassays for dinitrophenols in

water have been obtained. Work plans are underway to incorporate

iodine-125 into the technique to provide a more specific procedure

of antibody labeling.

80 BCLa - ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

Under the task, " Development of SRM's for Stationary Sources

Associated with Energy Production", mixtures of NO

2 in air at 250,

500, 1000, and 2500 ppm were evaluated for homogeneity; cylinders

vii
of 50 and 90 ppm SC>

2 in N

2 have been ordered, and prepared laboratory standards of these are under evaluation; and two new SRM's

of 2 and 10 mole-1 0

2 in N

2 have been certified. Under " Development

of SRM's for Monitoring Ambient Air Impacted by Emissions Resulting

from Energy Production ", gravimetric standards of C0

2

in air at

atmospheric concentration had a total estimated uncertainty not

exceeding ±0.1 percent relative; two additional Computer-Operated

Gas Analysis Systems (COGAS-II and COGAS-III) were constructed,

one to assist gas SRM certification, the second for automation of

gas permeation tube calibrations; and a procedure for establishing

traceability of commercial gas standards to NBS gas SRM's was

reviewed by EPA (EMSL/RTP) and representatives of the Compressed

Gas Association.

In the development and evaluation of standards for calibration of

x-ray fluorescence particulate analysis, thin films were prepared

from glass targets having low Z elements (S,P), and additional

glass targets containing 5-6 elements of interest to EPA (having

various elemental compositions) are under evaluation.

Under " Particulate Physical and Chemical Characterization", work

on Particle Doppler Shift Spectrometry (PDSS) is heading into the

submicrometer aerosol particle range, a developed theoretical

model was found to agree well with experimental results, and PDSS

was used to characterize several aerosol generatofs. Also, it

was found that aerosol size of solid spherical particles generated

from ammonium fluorescein solution by a vibrating orifice generator

can be predictable.

Under " Particulates on Glass Fiber Filters ", final certification

of SRM 2673 (Sulfate and Nitrate on Filter Media) and SRM 2674

(Lead on Filter Media) was completed.

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The bulk urban air particulate collection for Washington, DC, was

completed, and the material was sieved and subjected to preliminary

analyses for inorganic and organic constituents.

80 BCLb - ENERGY RELATED AIR POLLUTANT ANALYSIS INSTRUMENTATION

Under " Development of an Instrument to Measure Airborne Sulfate

Particulate Matter”, detector response was shown to be consistent

with theory, and sensitivity was enhanced using a sulfur compound

to dope the detector hydrogen gas. Further, it was shown that an

alternate detector design could improve response time by a factor

of 15, allowing for essentially full recovery of the potentially

available response.

80 BCLc - ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

Under "Radiocarbon as an Environmental Trace ”, using the MBS

system for analysis of environmental samples containing only 5-10

mg carbon in several collaborative studies with industry and

universities, it was generally observed that (1) urban particulates

predominantly contain fossil carbon, and (2) particulates from

remote locations contain less organic carbon (which is primarily

biogenic) . An exception to this was found in a study of air

particulates in Portland, Oregon that were found to contain up to

100 percent biogenic (natural) carbon, illustrating an air

pollution potential due to residential wood burning. In addition,

collaborative work is underway for calibration of the new MBS

International Radiocarbon Dating Standard for high accuracy radiocarbon measurements. Other advances have included the initiation

of analysis of atmospheric methane, and the use of a tandem

Van de Graaff accelerator to demonstrate a significant lowering

of sample size requirements for measuring natural radiocarbon to

10 micrograms of carbon.
Under " Organics on Air Particulates ", methodology has been

developed and refined for quantitative characterization of

polycyclic aromatic hydrocarbons (PAH) extractable from the NBS

Urban Air Particulate SRM (SRM 1648) . Various extraction

procedures have been evaluated. Analytical methodology is based

on normal phase HPLC fractionation, followed by analysis of the

isolated PAH fractions by capillary column GC/MS, and by

reversed-phase HPLC with fluorescence detection. Over 50 PAH

derivatives have been identified.

80 BCMa - ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

The task, "Energy Related Water Pollutant Standard Reference

Materials " , was initiated to develop energy related water pollutant

Standard Reference Materials (SRM's) for conventional fossil fuel

mining and combustion fuel technologies, with the Western areas

of the U.S. being the primary focus of studies/activities. Work

this reporting period focused on the completion and certification

of Standard Reference Materials for Estuarine Sediment (SRM 1646) , a re-issue of Trace Elements in Water (SRM 1643a), and Polynuclear

Aromatic Hydrocarbons (SRM 1644) is in process.

Preliminary experiments with Matrix Isolation Laser Raman Spectroscopy have shown this technique to be technically and scientifically

feasible for sequentially acquiring and analyzing data for complex

mixtures of volatile orgailics. Efforts are underway to refine this

technique so that it could be applied to the certification programs

for SRM's for Trace Organics in Water.

80 BCMb - ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

Activities under this task focused on the development of SRM's

for organic water pollutants associated with emerging energy

technologies. Significant progress was made on the analysis of

x
phenolic species in shale oil using several analytical techniques.

More developmental work (e.g. stability studies, method refinement)

leading to the production of a phenol in water SRM has been

performed during this reporting period.

NBS participated in a round robin exercise to determine interlaboratory precision on the measurement of phenols in waste

waters. The phenol concentrations and pHs found for eight samples

are reported.

80 BCN - ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVLEOPMENT

Activities under the task, " Radiological Pollutant Quality

Assurance " , resulted in the preparation and submission (to EPA/

Las Vegas) of two hundred samples of fly ash assayed for

radium-226 and radium-228. NBS also provided EPA/LV with seven

solution reference samples as part of the measurement traceability

program conducted with the EPA/LV laboratory.

xi

80 -BCK- a -ENERGY RELATED POLLUTANT MEASUREMENT AND INSTRUMENTATION

AND DEVELOPMENT

1 . Energy-Related Water Pollutant Analysis Instrumentation

1 . a . Development of Marker Compounds

A revised list of 23 labelled compounds to be used in the Master

Analytical Scheme (and samples of two additional compounds) were

received in mid-December. One labelled (quinoline-dy) and two

unlabelled compounds (bisphenol A and di-n-octyl ether) to be

provided by Research Triangle Institute/Gulf South Research

Institute (RTI/GSRI) have not yet been received.

Plans have been made for the preparation of the required 600

vials of six spiked solution mixtures, and for studies of the

stability of the six mixtures.

Synthesis of Labelled Compounds . Two labelled compounds were

to be synthesized by NBS. 2 -Naphthalene sulfonic acid-dy has

been prepared with a mass purity of greater than 99 percent (as

determined by HPLC) and an isotopic purity of 98 percent (by

mass spectrometry) . Unlabelled dodecylphosphoric acid has been

prepared from dodecanol as a model for the preparation of

dodecylphosphoric acid-d

2 ^ from dodecanol-dy^.

Chemical and Isotopic Purity of Marker Compounds . Table 1 lists

the current status of the chemical and isotopic purity checks.

Six compounds that were dropped in the latest list of marker

compounds, but for which data had been acquired, are not included.

Chemical purity has been checked by gas chromatography (GC) or

liquid chromatography (LC) for quantitative data and also by mass

spectrometry. Isotopic purity has been checked by mass spectrometry with results listed as satisfactory (S) since numerical

values have not yet been calculated from the mass spectra.
Table 1

Current Status of the Chemical and Isotopic Purity Checks

Chemical Purity Isotopic

Compounds Available Quant. Method % Impurities Purity

n - Butyl amine -dg S

n-Butyric acid-dy

2-Naphthalenesulfonic acid-dy

Dodecylphosphoric acid-d

2 3

Ethanol-d^ a Acetonitrile-dg

t-Butanol-d^

Q

a

1 , 2 -Diehl o roe thane -d^

Diethylether-d^g

Anisole-2 ,4 , 6-dg

Chlorobenzene -dg

n-Decane-d

2 2 Naphthalene -dg

o-Xylene~d10

Nitrobenzene -dg

Anthracene-d

10

Di -n- octyl ether -dg^

Quinoline-dy

Phene thyl amine -d^

Hexame thy lenetetr amine -d^

2 Phenol -d^ a Benzoic acid-dg

Bisphenol A-d^^ a

LC <11 S

GC <1% S

GC ND

GC S

GC ND S

GC <U S

GC ND S

GC ND S

GC ND S

GC ND S

GC ND S

S

GC ND S

GC ND S

S

GC ND S

S

ND = non-detected S = satisfactory

Isotopic purity checked/to be checked by H/D exchange with

water giving purity for ethanol-dg, t -butanol -dg , phenol-dg,

and bisphenol A-d^.

2
All of the compounds tested appear to be of satisfactory chemical

and isotopic purity for the intended purpose, except for

1 . 2

dichloroethane-d^ . This compound appears to be contaminated

with about 7 percent of 1 , 1 , 2-trichloroethane and 1 percent of

1 . 1 . 1 . 2

tetrachloroethane , as determined by electron capture GC

.

The presence of 1 , 1 , 2- trichloroethane-d^ was confirmed by mass

spectrometry

.

1 . b . Application of Selective Detectors to Liquid Chromatography

See Section BCK-a l.e.

1 . c . Liquid Chromatography-Mass Spectrometry

Changes made in the instrument since the last report include:

installation and calibration of a sensor (to better determine the

ion source temperature) , changes in the heat sink at the probe

tip (to find the optimum configuration) , and replacement of one

of the vacuum flanges with a viewport and telescope (to permit

viewing the operation of the LC-MS interface probe in_ situ )

.

A determination of the maximum flow rates that the concentrator

could accommodate was made and the results are shown in Table 2.

LC/MS of heterocyclic compounds containing nitrogen gave the

expected chemical ionization spectra at high source pressures,

and spectra with more electron impact El character at lower

source pressures.

Table 2. Concentrator Flow Rates

Solvent

n-pentane

i -octane

Methanol

50% Methanol/H^O

AHva

90 cal/g

90 cal/g

260 cal/g

410 cal/g

aHeat of vaporization.

Maximum Flow Rate

3.0 mL/min

2 . 8 mL/min

1.7 mL/min

0.7 mL/min

3
Preliminary tests have been made with encouraging results for

the direct determination of phenol in shale oil. The selectivity

of the mass spectrometer as an LC detector enables us to obtain

a clean phenol peak by monitoring at m/ z = 94. The first determinations yielded a value that is about 10-20 percent higher than

was obtained by other methods, but the stability of the response

of the instrument is excellent, promising usefulness as a quantitative detector. (For example, the standard deviation of

replicate standards is about 5%.) Comparison of the ultraviolet

(UV) 254 nm chromatogram and the m/z=94 LC/MS single ion record

obtained under identical HPLC conditions is made in figure 1.

When running direct injections of shale oil, some problem was

experienced with the deposition of material on the end of the

probe. A new end fitting has been designed but not yet constructed, using a Teflon diaphragm on the end of the probe. The

flow control needle will perforate the soft material and it is

hoped that the resulting orifice will be smaller and smoother so

that the momentum of the exiting liquid will be sufficient to

tear the liquid drops away from the end of the probe.

A description of the LC-MS concentrator and probe was presented

at the American Society for Mass Spectrometry meeting in

Seattle; and a patent application for the interface has been

filed by EPA.

1 . d. Feasibility Study of Application of Particulate Analysis

by Ion Microprobe

No report issued for this report period.

4
Figure 1. UV and MS chromatograms from direct HPLC injection

of 1 microliter of shale oil containing 400 ppm of

phenol.

5
1 . e . Liquid Chromatograph with Electrochemical Detection of

Or ganorne tal lie Compounds

Significant progress has been made in the development of electrochemical detectors for the measurement of trace organometall ics

Past work has shown that the best detection limits for reducible

analytes are obtained only through a laborious approach where the

entire liquid chromatograph is enclosed in an inert atmosphere

box. This was necessary to exclude all oxygen, which contributes

greatly to detector noise. However, a new detector described

below has been developed that allows work in a normal laboratory

environment without sacrificing the excellent detection limits

obtained in the inert atmosphere.

The new detection approach takes advantage of the electrochemical

behavior of the organotin cations:

The first reduction step can lead to two products, both of which

can be oxidized if the electrode is held at a positive potential.

The new detector cell is pictured in figure 2. The unique

feature is the use of two electrodes: the first electrode that

the L.C. effluent stream encounters is a generator electrode (G)

that is held at a potential sufficiently negative to reduce the

organotin cations. The flow then carries the products to a second detector electrode (D) which is held at a potential

appropriate to oxidize the products. The advantage of this

approach is that D can be poised at a potential where there is

no response for oxygen; thus, the background residual current

and noise are auite small. It is, however, prudent to remove

R^Sn

+

+ e R^Sn*

R^Sn* + R^Sn* R^Sn-SnR^

R^Sn* R^Sn

+ + e R^Sn-SnR^ -* 2R^Sn

+

+ 2e

E, £ -1.1 V

h

E, ^ -0.9 V

6
most of the oxygen from the solvent by simple purging of the

solvent reservoir, since the hydrogen peroxide formed on the

oxygen reduction could chemically oxidize the reduced oxganotin

products to an undetectable form.

Figure 3 shows a preliminary test of the new G-D cell with an

electrochemically well-behaved organic compound (anthroquinone)

.

The s ignal - to -noise ratio improvement with the new detector (on

left) compared to direct reduction (on right) is readily

apparent. The efficiency for the conversion and detection of

the analyte was estimated at 31 percent for anthroquinone.

Figure 4 shows the detection of trace amounts of three organotin

cations with the G-D cell. Limits of detection in the submicromolar range (10's of ppb) can be anticipated, even for these

difficultly reduced species.

Future work will evaluate the selectivity of this detector and

investigate the advantages of the use of modulated waveforms to

further increase the selectivity.

A detailed report ’’Assessing the Environmental Impact of FossilFuel Based Energy Sources: Measurement of Organometal Species

in Biological and Water Samples using Liquid Chromatography with

Electrochemical Detection” (by W. A. MacCrehan and R. A. Durst,

Center for Analytical Chemistry, NBS) was issued as EPA-600/7-

79-211 (November 1979). This was an Interagency Energy/

Environment R§D Program Report with the cover title: Assessing

the Environmental Impact of Fossil-Fuel Based Energy Sources.

7
A

Figure 2. Generator -Detector (G-D) thin layer cell.

1 Reference electrode, 2 Auxiliary electrode

(for detector) , 3 Assembly screw, 4 Solution

exit, 5 Auxiliary electrode (for generator),

6 Teflon spacer gasket, 7 Solution inlet,

8 Generator electrode (G) , 9 Detector

electrode (D)

.

8
* < * 1 I T J 1 0 i 2 3 0 12 3

Figure 3. Comparison of G-D cell response to that of

a single electrode cell. Left chromatogram:

G @ -0.7V D 0 +0.1V; right chromatogram

D 0 -0.7V. Both are 20 yL samples of 10 4 mol/L

anthroquinone on Spherisorb 0DS in 56 % CH 3 CN,

0.17 mol/L NH4 0 /Vc 0 1.0 mL/min.

9
Figure 4. Detection of organotin cations with G-D cell.

G @ -1.2V, D @ +0.1V. Left chromatogram:

1 x 10~ 4 mol/L (approx. 30 ppm) of each; right

chromatogram: 2 x 10 6 mol/L (approx. 600 ppb)

of nBy) 3 Sn , 3 x 10 6 mol/L (approx. 900 ppb) of

Et 3 Sn .

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l.f. Laser Enhanced Ionization

A detailed report is under preparation.

1 . g . Speciation of Inorganic Pollutants

Development of a measurement method to distinguish forms (specia

tion) of inorganic pollutants associated with energy related

effluents is necessary in order to assess the transport, transformation, and distribution of inorganic pollutants in the

aquatic environment.

Preliminary experiments in separation techniques, in particular

high performance liquid chromatography (HPLC) , and metal specifi

detectors have shown a high degree of promise for speciation.

Based upon this approach, work will be initiated to develop

methods for chromium and tin species.

11
80 -BCK-b- ENERGY RELATED WATER POLLUTANT ANALYSIS INSTRUMENTATION

1 . Development of Measurement Methods for Non-Volatile Organic

Pollutants in Water Due to Energy Technologies

1 . a . Raman Microprobe Characterization of Trace Polynuclear

Aromatic Hydrocarbons

The analytical goals pursued in this work fall along two lines:

1) The development of Raman microprobe techniques to permit the

analysis of microscopic volumes of effluents in liquid chromatography separations. The aim is to isolate sub-nanoliter

fractions of the chromatographic effluent stream, and to

determine the identity and concentration of the dissolved

analyte (s)

.

Various approaches are being explored to render practical microRaman detection with LC separation techniques. These involve

(i) trapping and isolation of effluent sampling volumes on

sapphire substrates or by adsorption onto high-surface area,

fine particulate solids (e.g., alumina); or, alternatively

,

(ii) isolation of the effluent in a microcapillary cell followed

by analysis of the liquid sampling volume.

The latter method appears to offer the most straightforward

approach. The Raman microprobe of present design permits the

efficient excitation/collection of Raman scattered light from

liquids confined to microcapillaries of 50 micrometers inside

diameter. Ongoing work seeks to define the limits of detection

for several of the common polynuclear aromatic hydrocarbons

(PAHs) present at low concentrations in the usudl liquid chromatographic solvents.

12
2) The Raman spectroscopic analysis of single particles of mass

in the sub-nanogram range to characterize and identify the

molecular forms and structures of the predominant inorganic and

organic compounds present in such samples.

This work entails the acquisition of a library of micro-Raman

reference spectra of environmentally significant chemical species,

including, among others, those containing the elements sulfur,

lead, vanadium, nickel, as well as inorganic and organic carbon.

In the speciation of carbon compounds, the detection and identification of solid-phase hydrocarbons is of particular interest,

especially with reference to their association with airborne

particulate material.

Work in progress centers on the acquisition and interpretation

of vibrational Raman spectra of laboratory-prepared samples, and

of unknown particulate samples collected from sources associated

with energy production and environmental degradation. Examples

are the spectroscopic characterization of polynuclear aromatic

hydrocarbons (PAHs) adsorbed as surface layers on inorganic

microparticles (i.e., alumina) and the analysis of particulates

produced in the combustion of fuel oils used in power generation.

1 . b . Development of Specific Immunoassays for Dinitrophenols

in Water

Work has focused on purification of specific antibodies required

for production of accumulator columns that have adequate affinity

for the ligand to which the antibodies were made. Continued

efforts to optimize small molecule immunoassay with titrated

antigens have not been fruitful; the binding is still low and

thus the precision is not adequate for reproducible assays.

13
It was postulated that significant non-specific binding reactions

could be minimized by fractionation of the rabbit sera to obtain

pure immunoglobulin (IgG) fractions. This has not been the case,

although relatively pure IgG fractions were prepared by ammonium

sulfate fractionation, gel- filtration, and ion-exchange chromatography. Affinity column purification of this purified material

has not been successful, possibly due to the low amounts of IgG

protein available for the columns.

The majority of the reagents for labeling the antibodies with

12 5

I have been obtained. We are presently identifying sources

for gamma counting and for data reduction. Other options

include labeling with fluorescein isothiocyanate or DTAF

(5- [4 , 6 -dichlorotriazin- 2 -yl-amino ] fluorescein hydrochloride) to

provide the basis for f luoroimmunoassay using photon-counting.

Finally, procedures have been selected for optimal coupling of

antibodies to solid phase support beads in anticipation of

more antibodies from rabbits that Will be immunized with

dinitrophenylated albumins over a longer time course than the

previously immunized rabbits.

14
80 -BCL- a- ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 . Development of SRM's for Stationary Sources Associated with

Energy Production

l.a. NO

2 in Air Gas Blend SRM's

The four levels of gas mixtures, 250, 500, 1000 and 2500 ppm NO^

in air, have been received and each batch has been evaluated to

determine homogeneity. The batches at 250 and 2500 ppm were

produced by one supplier and the batches at 500 and 1000 ppm

were provided by another supplier.

The results of the first set of intercomparisons are given in

Table 3.

Table 3

Intercomparisons of NC^ in Air Cylinders for Certification

Nominal

Concentration

(PPm)

Range of

Concentration

(PPm)

s.d. of the

Concentration

(PPm)

250 17 5

500 18 5

1000 12 3

2500 45 12

The lesser standard deviation relative to the range of values

reflects the fact that most samples had concentrations close to

the average but that in each lot there were several outliers. A

second analysis of all samples is essential to determine whether

the outliers represent unstable samples or samples whose concentration fell at a lesser value at the time of preparation.

15
The results are encouraging, however, since a larger spread in

the values was expected. A second analysis of the four sets is

scheduled to start during the first week of April 1980.

l.b. SO., in N~ SRM

Orders have been prepared for the purchase of 50 and 90 ppm S0

2 in N

2

. The laboratory standards necessary for the certification

of the 50 and 90 ppm SO

2

SRM's are being prepared and evaluated.

Both a chemical method (hydrogen peroxide method) and gas

chromatography will be used in the certification.

l.c. NO in N

2

SRM

No further work has been done since the issuance of the 1500

and 3000 ppm NO in N

2 SRM's.

l.d. 0

2

in N

2

SRM’s

Two new SRM's (SRM # 2657 and 2658) consisting of two and ten

mole percent 0

2

in N

2

have been completed. The material has been

turned over to the NBS Office of Standard Reference Materials

(OSRM) and the certificates are in preparation.

1

.

e . Stationary Source Gas SRM's

The anticipated time of completion of the final report on this

phase of the program is June 30, 1980.

2 . Development of SRM's for the Monitoring of Ambient Air

Impacted by Emissions Resulting from Energy Production

2 . a

.

Trace Level Reactive Gas SRM's

No report issued for this report period.

16
2.b. CO

2 in Air

Work on a set of 14 gravimetric standards has been completed.

The estimated uncertainty based on all recognized sources of

error does not exceed ± 0.1 percent relative (0.3 ppm) and is

probably somewhat less. Work is continuing to define this

error more absolutely.

Secondary standards for certification of SRM's have been

prepared and are being compared to the gravimetric standard.

An additional uncertainty due to the comparison process of

about ± 0.06 ppm will be assigned to the values of the concentration of the secondary standards.

2 . c . Automation of Gas Analysis

A second Computer -Operated Gas Analysis System (COGAS-II) has

been constructed, and is in use for certification analyses of

SRM's.

A third system (COGAS-III) has been constructed. This system is

intended for the automation of permeation tube calibrations, and

preliminary results indicate that the system will operate as

intended

.

2 . d . Development of a Traceability Procedure for Gas Standards

Preliminary reviews of a procedure for establishing traceability

of commercially prepared mixtures to certain gaseous SRM's have

been completed. A meeting with representatives of the gas

industry is planned for March, 1980 at which time the industry

will comment on the practicability of the procedure relative to

the state-of-the-art both of the preparatory processes and the

analytical procedures.

17
3 . Develop Methods for Dispersal of Particulates on Filter

Media and Methods for Determining and Controlling the

Composition and Morphology of Such Dispersed Particulates

3 . a . Thin Glass Films Produced by Focused- ion Beam Sputtering

Since the last report we have compiled our completed work to date

in a comprehensive report (now in press) . This report includes

our most recent work on the preparation of thin films from glass

targets prepared at NBS that contain elements of low atomic

number, such as sulfur and phosphorous. Plans for the remainder

of this year include fabrication of several glass targets (18 cm

diameter) , each containing elements of interest to EPA. The

proposed compositions of these targets are summarized in Table 4.

Table 4

Nominal Composition of Proposed Glass Targets (A-C) for 1980

(Percent Composition)

Compound A B C

Sl0

2 40 40 40

A1 2°3 10 10

Fe 2°3 10

V 2°5 5

CaO 10 10

PbO 20 20 20

B 2°3 5 10

Ti0

2

10

ZnO 10

Mn0

2 10

K 2° 10 4 Cr 2°3 5

CuC>2 5

18
These glass targets will be fabricated and characterized by NBS.

Several sets of films will then be prepared and characterized by

x-ray spectrometry and/or other instrumental techniques. Several

sets of characterized films will then be made available to EPA

for their use.

4 . Particulate Physical and Chemical Characterization

4 . a . Particle Doppler Shift Spectrometer (PDSS)

As indicated 'in the preceding report, a vacuum sample tube was

designed and installed in the PDSS in order to extend particle

size measurements into the submicron range. Although the vacuum

requirements are not extreme (down to a few torr) , the stability

of the system in holding a vacuum is critical due to the dependence of the slip correction and mean free path upon pressure.

Extensive leak testing has been completed during which several

components of the system (a pressure gauge and two high vacuum

valves) were found to be defective and were replaced. The system

is now ready to begin measurements of the slip correction and very

low Reynolds number air flow phenomena, and of submicron aerosols.

Experimental studies of the extremely small particle- induced

fluid flow phenomena (fluid flows of the order of 0.01 cm/s) have

been completed, and a theoretical model has been developed

through the exact solution of the Navier-Stokes equation in the

low Reynolds number regime. The theoretical model agrees well

with the experimental results. These studies are now being

prepared for publication.

The PDSS has been used to help characterize the properties of

several aerosol generators. Our experience with the spinning

disk generator shows it to be useful for generating mono-dispersed

dioctylphthalate aerosols in the size range greater than about 15

19
micrometers, but not as useful as the Berglund-Lui vibrating

orifice generator in the less-than 15 micrometer range.

Studies have also been made on the properties of ammonium fluorescein for use as an aerosol material. Aerosols generated by the

vibrating orifice from a solution of ammonium fluorescein are

solid, spherical particles, and have optical properties that allow

ready detection at trace levels by spectrophotometric techniques.

They have very low volatility and a high melting point, making

them suitable for electron microprobe and x-ray analysis. In

addition, ammonium fluorescein is considered to be non-toxic.

Measurement of the diameter of ammonium fluorescein particles

generated using the vibrating orifice generator has demonstrated

that the size of the aerosol can be predicted and controlled by

the molarity of the fluorescein solution used in the generator.

5 . Particulates on Glass Fiber Filters

5 . a . Certification of SRM's for Pb, Sulfate, and Nitrate on

Filter Media

Final certification of SRM 2673, Sulfate and Nitrate on Filter

Media, and SRM 2674, Lead on Filter Media, has been completed.

These materials are intended for use in the evaluation of

apparatus and methods used in the determination of lead, sulfate,

or nitrate in atmospheric particulates collected on filters.

Certification measurements for the anions were accomplished by

ion chromatography. Lead for SRM 2674 was determined by both

voltammetry and atomic absorption spectrometry (AAS) . Statistical

analysis of the data indicated no significant effects of biases

in the AAS due to undissolved solids from the glass filter matrix.

Copies of the certificates of analysis are included for

information.

20
U.S. Departriient of Commerce

Juanjta JJ. Krepe

'Nr' National Buraair of Standards

Ernest Ambler. pirector Rational bureau

Certificate of

of ^tanrfarrfg

(Analysis

Standard Reference Material 2673

Sulfate and Nitrate on Filter Media

This Standard Reference Material is intended for use in the evaluation of apparatus and methods used in the

determination of atmospheric particulate sulfate and nitrate which have been collected on filters. It consists of a

series of filter strips upon which sulfate and nitrate have been deposited in an essentially central location. 1 he

values certified correspond to the quantities of the substances leached from the filter strip without destruction of

the filter matrix.

Sample

Number

Sulfate content ng/ filter Nitrate content ^ig/ filter

Average value Tolerance limits Average value Tolerance limits

I 503 493 - 513 100 98 - 102

II 2002 1955 - 2049 1002 978 - 1026

III 6939 6635 - 7243 2513 2404 - 2622

Blank 2 0-6* 2

l • o

* Range of measured values The average value is the mean based on the analysis of 24 or 28 filters randomly selected from the lot. The

tolerance limits are determined so that at the 95% confidence level they will contain the central 95% of the

population of filter values. Details of the preparation, analysis, and statistical treatment of the data are given on

the reverse side of the certificate.

This Standard Reference Material was prepared by B. I. Diamondstone. The analytical measurements were made by W. F. Koch. Statistical analysis of the data was provided by J. Orban. The overall direction and

coordination of the preparation and analytical measurements leading to certification were performed in the Center for Analytical Chemistry under the chairmanship of J. K. Taylor.

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 W. P. Reed.

Washington, D.C. 20234

June 25, 1979

21

George A. Uriano, Chief

Office of Standard Reference Materials
Preparation

This SRM consists of strips cut from glass fiber filters, such as arc commonly used for measurements of

atmospheric particulates, using high volume samplers. Solutions containing known amounts of potassium

sulfate and potassium nitrate were prepared, gravimetrically, and multiple aliquots of 25 nL were placed on the

filter strips. Four aliquots were so transferred to each filter in the case of samples I and II, and five in the case of

Sample III. The pipets were calibrated by weighing similar aliquots transferred into weighing bottles. The filters were prepared in a clean room and allowed to air-dry before packaging in glassine envelopes. The

filters were prepared in groups of 100 and the proper number of aliquots were dispensed into weighing bottles at the beginning and end of each sequence, to monitor the performance of the pipet.

Analytical Measurements

Twenty four samples were randomly selected from the production lot (28 in the case of sample III) for chemical

measurement of their extractable sulfate and nitrate. Each filter strip was extracted with a standard eluent (see

below) for 15 minutes in a 55 °C ultrasonic bath. The extracts were analyzed for sulfate and nitrate by ion

chromatography. The eluent was a solution of 0.003 M NaHCC>3 and 0.00 1 8 M Na2 C(>3. A 100 /iL sample loop was used. Peak heights were compared with those obtained from accurately prepared standard solutions. Three

standards were prepared for each concentration level so as to bracket the extracts. The randomly selected filters were also analyzed in random order. No significant systematic errors were

observed related to the order of preparation. Average values and the overall standard deviation, so, of

individual measurements were calculated. This standard deviation includes measurement error and filter content error. The standard deviation, Sf, due to filter content variability was competed from a sample of 12 or 14 weighed

quantities delivered by the pipets during the preparation of the filters. The resulting tolerance interval for the

sulfate /nitrate contents is of the form

X ± k sf .

It is this tolerance interval that should be of greater interest to the participating laboratory since it gives practical

bounds for the likely values of the sulfate or nitrate contents that might be found in a given filter. The following table lists the values of so and sr for each set of filters. The measurement standard deviation, sm, for NBS can be computed using the relation so

2 = Sm2 + Sf2

Set Average (^g) So Sf so4 502.6 8.89 3.14

no3 100.3 2.56 .63 so4 2001.7 29.30 14.88 N03 1001.7 15.92 7.44

so4 6939.0 109.35 100.75

no3 2513.0 43.70 36.30

The average values calculated from the composition of the solutions and the quantitites delivered by the pipets are in general agreement with the analytical values. However, the values certified are those obtained by analysis.

Recommended Usage

The material is not homogeneously distributed on the filter; hence the sample must be used in its entirety for

analysis. It is recommended that the filter be extracted at 55 °C in an ultrasonic bath, with water or other

nonreactive solvents. The filter base should not be digested to put it into solution.

22
U.S. Department of Commerce

Juanita M. Kreps

Secretary r .

i National Bureau of Standards

Ernest Ambler. Director

Rational ^arsau of J^iatttlarde

Certificate of (Analysts

Standard Reference Material 2674

Lead on Filter Media

This Standard Reference Material is intended for use in the calibration of apparatus and the evaluation of

methods used in the determination of atmospheric particulate lead which has been collected on filters. It consists

of a series of filter strips upon which lead has been deposited in an essentially central location. The values

certified correspond to the quantities of the substance leached from the filter strip without destruction of the

filter matrix.

Sample No.

Lead Content, /zg/ filter

Average Value Tolerance Limits

1 100 97 - 103

II 303 294 - 312

III 1505 1477 - 1533

Blank 1.4 0.7- 2.1*

•Range of measured values The average value is the mean based on the analysis of 26 or 28 filters randomly selected from the lot. The

tolerance limits are determined so that at the 95% confidence level they will contain the central 95% of the population of filter values. Details of the preparation, analysis, and statistical treatment of the data are given on

the reverse side of this certificate.

This Standard Reference Material was prepared by B. I. Diamondstone. The analytical measurements were made by E. J. Maienthal and M. S. Epstein of the Inorganic Analytical Research Division. Statistical analysis of

the data was provided by J. Orban of the Statistical Engineering Division.

The overall direction and coordination of the preparation and analytical measurements leading to certification were performed in the Center for Analytical Chemistry under the charimanship of J. K. Taylor.

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. Washington, D.C. 20234 George A. Uriano, Chief

December 18, 1979 Office of Standard Reference Materials

2 3
Preparation

This SRM consists of strips cut from glass fiber filters of the type normally used in high volume samplers for the measurement of atmospheric particulates. Solutions containing known amounts of lead nitrate were prepared

gravimetrically, and aliquots of 25 /uL were placed on the filter strips using micropipets. Four aliquots were

transferred to each filter in the case of samples I and II and five in the case of sample III. The pipets were

calibrated by weighing similar aliquots transferred into weighing bottles. The filters were prepared in a clean room and allowed to air-dry before packaging into glassine envelopes. The

filters were prepared in groups of 100 and the proper number of aliquots were dispensed into weighing bottles at the beginning and end of each sequence, to monitor the performance of the pipet.

Analytical Measurements

Twenty-eight filters were randomly selected from the production lot (26 in the case of Sample I) for chemical

measurement of extractable lead. Selected filters were extracted with dilute nitric acid, using ultrasonic

vibration to assist in the extraction. After the nitric acid extraction, the filters were thoroughly rinsed with

distilled water to ensure complete extraction. The extracts were quantitatively diluted and analyzed by linear sweep voltammetry which had been calibrated with solution standards prepared from high purity lead. The selected filters were analyzed in random order. No significant systematic errors were observed related to order of preparation. Average values were calculated together with the overall standard deviation. So, of

individual measurements. This standard deviation includes measurement error and filter content error. The

resulting confidence interval for the mean is of the form

_____

i

» X±ts0 //~n\

where s0 is based on n - 1 =27 degrees of freedom.

A selected number of filters were also analyzed by atomic absorption. The results obtained were well within the tolerance limits given and were consistent with the certified values. The standard deviation, sr, due to filter content variability was computed from a sample of 12 or 14 weighed

quantities delivered by the pipets during the preparation of the filters. The resulting tolerance interval for the

lead content is of the form

X ± k sf.

It is the tolerance interval that should be of greater interest to the participating laboratory since it gives practical

bounds for the likely values of the lead content that might be found in a given filter. The following table lists the values of s0 and Sf for each set of filters. The measurement standard deviation, sm, for NBS can be computed using the relation s0

2 = sm2 + Sf2

Set Average (^g) So Sf

I 99.7 1.59 0.89

11 302.9 5.37 3.00

III 1505.2 12.73 9.24

The average values calculated from the composition of the solutions and the quantities delivered by the pipets are in general agreement with the analytical values. However, the values certified are those obtained by the

analysis.

Recommended Usage

The material is not homogeneously distributed on the filter, hence the sample must be used in its entirety for

analysis. It is recommended that the filter be extracted at 45-50 °C in an ultrasonic bath, with dilute nitric acid (2

mL HNO3 + 1 5 mL H2 O). After extraction the filters should be thoroughly rinsed with distilled water. The filter base should not be dissolved.

24
6 . Urban Air Particulate, Washington, D. C. Sample

In August 1979, the collection of the Washington, DC, urban

particulate sample was terminated. The bags were vacuumed out

using the same system as that described for the St. Louis

material, and approximately 45 pounds of unsieved material was

obtained. Several sieving strategies were evaluated in order to

develop one that was effective in removing bag fibers, but did

not excessively reduce the non-bag fiber fraction of the sample.

It appears that 30-35 lb. of sieved material will be available

for final analysis. Preliminary inorganic, organic, and particle

size analysis has been performed on the Washington material. The

analysis indicated that the Washington material can be used either

as a replacement for the St. Louis material or as an organic

certified sample. A final decision regarding the Washington

material will be made toward the end of FY-80, after additional

information on the sales of SRM 1648 (St. Louis material) and the

preliminary organic analysis of the Washington material are

completed

.

Some preliminary work has been performed on converting the baghouse facility to a system to collect only respirable particulate

material. Discussions with various EPA laboratories indicated

that this was the highest priority need for further collection

studies. It is anticipated that these respirable particle

collection feasibility studies will be completed by the end of

fiscal year 1980.

7 . Develop SRM's for Coal Conversion Processes and Materials

Balance Determinations

No report issued this report period.

25
8 . Development of an Oil Shale SRM

As previously reported, a quantity of Oil Shale SRM has been

sterilized and set aside for comparison with unsterilized Oil

Shale to determine if there are any changes in the concentration

of volatile substances, both organic and inorganic. However, a period of prolonged down-time for the NBS reactor has delayed

further research on this material.
80 -BCL-b -ENERGY RELATED AIR POLLUTANT ANALYSIS INSTRUMENTATION

1 . Development of an Instrument to Measure Airborne Sulfate

Particulate Matter

Work has continued on the characterization and optimization of

the pulsed precipitator/flame photometric detector (FPD) aerosol

sulfate measurement technique. As indicated in the preceding

report, we made an evaluation of the feasibility of doping the

hydrogen gas with SO ? or ethyl mercaptan in order to increase

the total FPD response into a range where the instrument is more

stable, and to increase the sensitivity of the response. The

sensitivity of the system is a function of the total signal,

because the FPD response (R) is nonlinear with sulfur concentration^) ; (i.e., R<*[S] n

, where n = 1.8, therefore Sens. = a n[S]). We have experimentally verified this prediction; viz., an

increase in total sulfur concentration of a factor of 2.6 is

predicted to give an increase in sensitivity of 4.7, in good

agreement with an observed increase of 5.1.

An important limitation in the application of the FPD for airborne

sulfate particulate measurement is the slow response time of the

burner to changes in sulfur concentration. The rise time for 90

percent of full equilibrium response is about 15 seconds, and

the fall time is 2.8 seconds. For a precipitator operating

frequency of 0.2 Hz we can obtain only 60 percent of the potentially available response. This is equivalent to a loss in

sensitivity of almost 50 percent. We therefore have looked for

better burner designs. We recently evaluated a burner and

detector system built by Dr. Don Stedman at the University of

Michigan and found that it was much faster (rise time = 1 sec;

fall time - 0.2 seconds). We will obtain this instrument through

a collaborative study arrangement, evaluate the burner for

sensitivity, and optimize it for application with the pulsed
precipitator technique. Table 5 shows a comparison of the

percent of full response vs. precipitator frequency for the

instrument we have been using, and for the University of

Michigan burner/detector.

Table 5

Recovery of Potentially Available Response vs. Precipitation

Frequency

Frequency (hertz)

.2

. 5

1.0

2.0

4.0

Percent of Full Response

Meloya FPD U. of Mich. FPD

60

17

5

2

100

85

65

30

10

cl In order to adequately describe materials and experimental

procedures, it is occasionally necessary to identify commercial

products by manufacturer's name or label. In no instance does

such identification imply endorsement by the National Bureau of

Standards nor does it imply that the particular products or

equipment is necessarily the best available for that purpose.

28
80 -BCL-c -ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 . Radiocarbon as an Environmental Trace

1 . a . Applications

The use of miniradiocarbon measurements with 5-10 mg (carbon)

environmental samples (gases, atmospheric particles, sediment)

has continued with the objective of utilizing the natural C/ C

ratios to distinguish between biogenic and fossil pollutant

sources. Important progress has been made in our understanding

of the source of carbonaceous particles, especially of those

collected in urban areas, through several cooperative studies

with industry* and universities**. A critical element in these

investigations has been the utilization of sample selectivity

(chemical and physical) in combination with the radiocarbon

measurements. That is, because small samples can be used, we

have been able to increase the "information content" of our

measurements by examining samples that have been preselected

according to geographical region, known activities, chemical

nature, and stable isotopic composition. A summary of our

recent radiocarbon results, together with an indication of these

critical supporting data, is given in figure 5. The general

conclusions to be drawn from these studies are (i) urban particles

tend to show predominately fossil carbon (though with a nonnegligible biospheric contribution) ; and (ii) particles from

remote locations contain less organic carbon, which is primarily

biogenic. An extremely important exception occurred in the

* General Motors, Global Geochemistry Corporation.

** Oregon Graduate Center, Colorado School of Mines, University

of Washington.

29
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30
Portland Study***, where the combustion of biospheric material

(field, slash, and residential wood burning) led to the first

observations of urban carbonaceous particles containing up to

100 percent biogenic carbon. These results have caused us to

focus on the air pollution potential of residential wood combustion — a problem which will be a subject of our continuing

studies (see figure 6)

.

1 . b . Research Advances

Research activities have been directed toward the analysis of

atmospheric gases, high accuracy natural radiocarbon measurements,

chemical -mathematical investigations of the Radiocarbon Dating

Calibration Curve, and extension of the state of the environmental radiocarbon art to microgram samples using Accelerator

Mass Spectrometry. Work with the atmospheric gases is still in

the initial stages; thus far milligram quantities of atmospheric

methane  have been extracted for radiocarbon measurement.

High accuracy radiocarbon measurements are underway in connection

with calibration of the new NBS International Radiocarbon Dating

Standard, and concomitant chemical - statistical investigations

have been performed in cooperation with the Australian National

University on an International Laboratory Intercalibration

exercise involving some 20 laboratories and three calibration

materials (Oxalic Acid, 1850 Tree Rings, Sucrose). Evaluation of

the fluctuations of the Radiocarbon Dating Calibration Curve is

underway in cooperation with the Statistical Engineering Division

** * The Portland Aerosol Characterization Study measurements

were carried out in cooperation with the Oregon Graduate

Center and the Oregon Department of Environmental Quality.

**** The methane study, of interest for climatic reasons and to

learn about man's perturbation of the carbon cycle, is being

carried out in cooperation with NOAA (Air Reserves Lab)

.

31
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32
of NBS under the auspices of an international committee formed

for this purpose. Information to be derived includes the assessment of accuracy, development of an accepted calibration curve

for accurate dating, and geophysical model information for the

assessment of past climatic variations (figure 7) . Studies

initiated in 1979 show outstanding promise for the analysis of

extremely ’’old'* and extremely small samples. Our exploratory

work, which utilized the NBS variable geometry isotope separator

and the University of Rochester Tandem Van de Graaff Accelerator,

demonstrated the feasibility of measuring natural radiocarbon

in the 10 yg range. All of the above activities are intended

to increase our ability to extract reliable information on

anthropogenic and natural contributions to both environmental

pollutants and chemically- induced climatic perturbations, now and

in the past.

2 . Organics on Air Particulates

In a previous report (FY-78) we described analytical methods for

the isolation, separation, and identification of polycyclic

aromatic hydrocarbons (PAH) in urban air particulate matter.

These methods have been employed for the qualitative characterization of the PAHs on SRM 1648 (Urban Air Particulate Matter)

.

An important part of this methodology is the use of normal phase

high-performance liquid chromatography (HPLC) on an aminosilane

column to isolate PAH fractions according to the number of

condensed aromatic rings [Anal. Chem. £9, 2306 (1977)]. The

normal phase liquid chromatogram of the analysis of the urban air

particulates (SRM 1648) is shown in figure 8. Each of the

numbered fractions was then analyzed by gas chromatography/mass

spectrometry (GC/MS) and reverse-phase HPLC with fluorescence

detection for identification of the PAH. The GC analyses of

fractions 3, 4, and 5 are shown in figure 9. The isolation

of PAH fractions in this manner allows identification of many

33
CONVENTIONAL

RADIOCARBON

DATES

IN

RADIOCARBON

YEARS

BEFORE

PRESENT

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34
Inject

Urban Air Particulates - Normal Phase HPLC

uv

0 10 20 30 40 50 60

TIME ( min j

Figure 3. Normal phase liquid chromatogram of PAH extracted from

urban air particulates. Column: semipreparative

y Bondapak NH 2 . Detection: UV absorbance at 254

nm. Conditions: n-hexane at 1 mL/min. Numbers

indicate f ract ions~~collected for subsequent

analysis and the PAH structures indicate elution

times for these representative compounds.
Fraction 5

Fraction 3

figure 9

L

Has chromatograms

of fractions 3, 4,

and 5 from urban

air particulates,

(see figure 8)

Column: SE-54

1VC0T glass capillary, temperature

programmed from

200-270° at 2°/min.

36
minor components in the mixture which would otherwise be obscured.

The PAHs identified in SRM 1648 are summarized in Table 6.

Reverse -phase HPLC analyses of the fractions using fluorescence

detection confirmed the identities of many of the PAHs. The

liquid chromatogram of the analysis of fraction 4 is shown in

figure 10.

Several different organic solvents have been investigated for

ultrasonic extraction of the PAHs from the particulate matter

(i.e., cyclohexane, methylene chloride, methanol, and tetrahydrofuran) . There are numerous reports in the literature of

the use of cyclohexane for these extractions. In our studies

the polar solvents appear to be more effective in removing the

PAHs from these particulates. However, these solvents also

remove additional organic compounds (i.e., those more polar than

PAHs) which create additional problems in the isolation of the

PAHs. The analytical methodology is being modified to solve

these problems.

37
Table 6

PAH's Identified in Urban Air Particulate Matter

(SRM 1648) a

Fraction 2

Phenanthrene D

Anthracene^

Methylphenanthrenes/anthracenes (4)

(probably methylphenanthracenes)

4H-cyclopenta(def)phenanthrene

C

2 -phenanthrenes/anthracenes (6)

Methyl - 4H-cyclopenta (def) phenanthrene

Fraction 3

L

Fluoranthene 0

Pyrene*5 Methyl fluoranthenes /pyrenes (5)

Benzo [a] f luorene

Benzo [b] f luorene *

C

2 -Fluoranthene/pyrenes (2)

Benzo [b]naphtho [2 ,1-d] thiophene

Benzo [c]phenanthrene

Benzo[ghi] fluoranthene

Cyclopenta [cd]pyrene

Benz acenaphthylene

Unknowns of molecular weight 230 and 234

38
Table 6 continued.

Fraction 4

L

Benz [a] anthracene 0

Chrysene*3

Triphenylene**

Methylbenz [a] anthracenes/chrysenes/triphenylenes (3)

(1-methyl-, 2-methyl-, and 3 -methylchrysene) 0

Binaphthyls (3)

C

2

-benz [a] anthracenes /chrysenes/ triphenylenes (2)

Methylbinaphthyls (3)

Quarterphenyl

Unknowns of molecular weight 240 and 278 (3)

Fraction 5

L

Benzo [b] fluoranthene 0

Benzo [k] fluoranthene*1 Benzo [e]pyrene°

Benzo [a] pyrene

0

Perylene**

Fraction 6

L

Indeno [1,2, 3 -cd] pyrene

0

Benzo [ghijperylene*1

Identities of specific isomers based on mass spectra and gas

chromatographic retention time.

^Identity confirmed by HPLC and fluorescence spectroscopy.

39
Urban Air Particulates - Fraction 4

Reverse Phase HPLC

Figure 10.

7,° 8.° 90 100 % CH,CN in WATER

l

•

1 1 -f— 1 0 10 20 30 40 50

TIME ( min )

Reverse phase liquid chromatographic

analysis of fraction 4 from urban air

particulates (see figure 8)

.

Column: Vydac 201TP reverse phase.

Detection: UV absorbance at 254 nm.

Conditions: linear gradient from 70-100

percent acetonitrile in water at 1%/min

at 1 mL/min.

40
80 -BCM- a -ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 . Energy Related Water Pollutant Standard Reference Materials

1 . a . Complete Certification of Ocean Sediment SRM

There has been no activity in this project during the reporting

period.

1 .b . Complete Certification of SRM 1646, Estuarine Sediment

Certification analyses for SRM 1646, Estuarine Sediment, are

mostly complete. The residual analytical effort, statistical

analysis of the data and final certification are likely to occur

during the next reporting period.

1 . c . Trace Elements in Water, SRM 1643

Statistical analysis of the trace element data for SRM 1643a

(re-issue) revealed the need for some additional study of

arsenic. Pending the completion of this work, final certification and availability of the SRM are anticipated during the next

reporting period.

1 • d . Aqueous Polynuclear Aromatic Hydrocarbon Standard SRM 1644

In previous reports, generator column technology was described

as an ideal technique for preparing saturated standard solutions

of individual polynuclear aromatic hydrocarbons (PAHs) . Certification of generator column standards for benzo (a)pyrene

,

benz (a) anthracene , and anthracene are in process.

41
2 . Matrix Isolated Laser Raman Identification of GC Effluents

A new, primary laboratory measurement technique is being developed

for the analysis and certification of Standard Reference Materials

and the performance of referee-type measurements of regulated

trace organics in water. This new method involves laser Raman

scattering from pollutants isolated in cryogenic matrices.

Over the past several months we have demonstrated the technical

and scientific feasibilities of sequentially acquiring and

analyzing complex mixtures of volatile organics such as those

currently being regulated by the EPA. Our diagnosis, laser

Raman spectroscopy of matrix isolated samples, should provide a molecular specificity and sensitivity comparable to, or better

than, existing techniques utilized for water quality assessment.

For example, in analyzing sample mixtures of isomeric species

such as the dichloroethylenes , it has been demonstrated possible

to correctly identify the mixture components, even when one

component was present in a large excess of another. In addition,

scaling laws for quantification, such as signal dependence on

laser power, sample concentration, deposition time, mixture

purity, etc., have been extensively studied. Of significant

note is the ability to qualitatively determine all components of

even very complex mixtures by their characteristic Raman signatures. Inherent in the matrix-isolation technique is the

independence of the signal from one component due to the

presence or absence of other pollutant species in the same

sample

.

Our previous efforts have been concerned with laboratory samples

and manual realignment of deposition source, new matrix sample,

and spectrometer.

42
When fully automated, our GC-cryostat should provide the capability for quantitative analysis of real-world water samples. Our

present efforts have been in upgrading our system to be used as

an analytical tool. We have initiated procurement for a dedicated

GC system for initial separation and sample acquisition; obtained

plans for the modification of our existing cryostat to be compatible with automatic sample acquisition and analysis; and

procured and interfaced a computer -controlled optical multichannel analyzer (OMA) to decrease analysis time and to allow for

spectral analysis, comparison to library stored references, and

quantitation of signal strengths to give an accurate analysis of

the purity of each successive water sample.

The GC under consideration is a capillary system with standard

FID. It will be possible to modify this system to interface to

the vacuum chamber of our cryostat. The GC effluent (i.e.,

separated pollutants in an excess of argon carrier) will enter

the sampling chamber through capillary tubing and impinge on an

octagonally-shaped gold-coated cold finger maintained at 14 °K.

- 2 2 The sample will condense in an area of approximately 10 cm . The cold finger will be rotated about a screw axis by an external

servo -control to present a new region for subsequent sample

deposition; the previous sample being moved into the interrogation region for the Raman spectrometer. Each sample is analyzed

as subsequent samples are acquired. The identity, composition,

and concentration of each sample is recorded in the computer

memory. The computer-controlled OMA allows for spectral acquisition in a few seconds that currently takes 10-30 minutes in our

single channel system. There will be room for approximately 48

samples on the cold finger. These samples may either be obtained

from subsequent (different) portions of the GC effluent of a single water sample extract, or a single cut, representing

particular retention time windows from each of a number of

different water sample organic components. When the cold finger

43
has been fully analyzed it is renewed by simply flash heating

in vacuo and re-cooling—a process requiring 10-20 minutes. Up

until the time of such a clean-up procedure any given sample

locus can be re-examined under high resolution Raman, or for an

extended period of time to test for very low levels of a given

pollutant, or to clarify an analysis.

44
80 -BCM-b -ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 . Develop Organic SRM's for the Calibration of Energy-Related

Water Pollutant Measurement Methods

l.a. Coal Conversion

There has been no activity in this project during the reporting

period

.

1 . b . Analysis of Phenolic Species in Alternate Fuels and

Effluents

As part of a project to certify a shale oil SRM and to develop

methods for quantitating trace levels of important organic

compounds, phenol and o-cresol concentrations in a shale oil have

been determined by gas chromatography-mass spectrometry with

selected ion monitoring. High performance liquid chromatographic

fractionation of the shale oil on a semi -preparative scale

aminosilane column was used to obtain a 'phenolic' fraction which

was free from other interfering compounds in the shale oil matrix

(the use of HPLC for the fractionation of shale oil has been

described in previous reports) . Additional specificity and

enhanced precision were achieved with the use of selected ion

monitoring (SIM) gas chromatography-mass spectrometry. Gas

chromatographic separations were carried out on specially prepared

wall-coated open-tubular columns coated with Pleuronic L-64.

This liquid phase separates compounds based on their polarity, and

provides excellent resolution of the C^-C^ substituted phenols

detected in the shale oil (see figure 11) . The superior resolution, along with the specificity of selected ion monitoring,

allows accurate quantitation of phenols in a complex matrix such

as the shale oil.

45
A standard addition method was used for quantitation. The molecular ions for phenol (m/e 94), (D-cresol (m/e 108), and m + ]D-cresol (m/e 108 monitored as a volume correction standard to

compensate for variable injection volumes) were monitored in

0.

1 amu increments (to insure that the voltage is sampled at the

peak maximum); see figure 12. Peak areas for the analyte and the

volume correction standard were integrated, and ratios of the

analyte/volume correction standard plotted vs. the concentration

of analyte added. The concentration of the analyte in the shale

oil was then determined from the ordinate intercept (see figure

13) . Nine standard addition experiments were run to test

homogeneity of the shale oil sample. The results of these determinations, shown in Table 7, compared favorably with values

determined independently by a gas chromatographic method.

Table 7

Phenol and 0-cresol Concentrations in Shale Oil

Method: GC/MS GC

phenol = 407 ± 37 ppm

a (n=9) 401 ± 9 ppm (n=8)

<3-cresol = 382 ± 40 ppm (n-9) 384 ± 20 ppm (n=8)

95 percent confidence limits (2o)

.

1

.

c . Development of a Phenol in Water SRM

Determination of individual phenols in environmental samples is

of particular interest because many substituted phenols have been

found to be toxic to aquatic life. Phenols are present in a wide variety of chemical processes, either as end products or as

intermediates. It has therefore been necessary to develop an

analytical procedure for the determination of phenols in water.

To date, a literature search has been made to obtain pertinent

information on the characteristic behavior of phenols in water.

46
r

I

47
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x)

d>

+-* cdCOu

cd

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—\ f-< £P U E ^

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CD <P E o

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48
II

II

II

II

II

II

II

II

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II

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III . rw

CL OnrbO

UJ

Q.to

•HO0

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49
In some of our earlier studies (reported previously) on the

stability of aqueous solutions of phenols, losses possibly due

to adsorption and biodegradation have been found. Due to these

results, it is essential to conduct a study of stability of some

carefully selected phenols in a distilled water matrix to

ascertain the possibility of an SRM.

1 . d . Interlaboratory Comparison

During the past six months NBS participated in a round robin

exercise to determine interlaboratory precision in the measurement

of phenols in wastewaters. Eight samples containing phenol were

received from ASTM. These samples were to be analyzed for phenols

using the procedure described in ASTM D1783, and the pH of the

samples was to be measured also. Preliminary determinations were

made on the samples in order to find the approximate phenol concentration. A thousand-fold dilution was required in order to

bring the concentration into the range for which the procedure

is valid. Concentrations and pHs found for the eight samples

follow in Table 8.

Table 8

Phenol Concentrations

Sample No.

Determination A

(mg/L)

Determination B

(mg/L) PH

1 40 40.4 8.5

2 20 20 4.1

3 3520 3710 8.8

4 65.2 66.4 8.4

5 35.8 35.6 4.1

6 4520 4520 8.8

7 2900 2950 3.7

8 124 127 4.0

50
80-BCN-ENERGY RELATED POLLUTANTS AND EFFECT MONITORING AND ASSOCIATED

METHODS AND TECHNIQUES DEVELOPMENT

1 . Radiological Pollutant Quality Assurance

The assessment of regional and national effects of radionuclides

depends on the comparability of empirical data generated throughout

the new energy developing industries as well as the existing nuclear

power industry. The major goal of this program element is to develop

an optimum radiological monitoring program to provide validated radiological environmental quality baseline data in those geographical areas where new energy developments impact on the environment.

The primary objective of the NBS program is to provide measurement

traceability, for certain radionuclides not included in other programs,

to the U. S. Environmental Protection Agency at Las Vegas (EPA-LV)

and, through EPA-LV, to other laboratories . Specific radionuclides

are chosen for the program because they are released into the environment from nuclear power reactors (such as light-water reactors), coal

burning plants, or other related sources.

1 .a Solution of Plutonium - 241

We are continuing to measure the half life of plutonium-241 by

means of a-y-coincidence measurements of the in-growth of

americium-241. Our results to date are consistent with the

generally accepted value of 14.35 years.

1 .b Fly Ash from Coal Combustion Assayed for Radium-226 and Radium-228

Two hundred samples of 100 grams each were sent to EPA-LV. The

Report of Calibration has been completed and submitted to EPA-LV

for distribution with the fly ash. A copy is attached as Appendix 1.

l.c Thorium-232 Solution

At the request of EPA-LV in October, NBS assayed the thorium-232

solution for radionucl idic impurities. Radium-226 was assayed by

gamma-ray spectrometry cf its shorter-1 ived progeny in equilibrium

with radium-226. Thorium-230 is being assayed by alpha-particle

spectrometry . The assays and the preparation of the Report of

Calibration should be completed during the first half of 1980.

51
1 .d Mixed Radionuclide Solutions

Two mixed radionuclide solutions have been prepared, each containing

tritium, strontium-90, cesium-134, radium-226, radium-^228, and

uranium of natural isotopic composition. One solution is a tenfold dilution of the other. Two hundred 5-ml ampoules of each

solution have been produced for distribution by EPA-LV. Checks on the production of these standards are underway, and the Reports of

Calibration are being written.

2 . Measurement Traceability Studies with Analytical Quality Control

of EPA-LV

The NBS conducts tests with Analytical Quality Control (AQC),

formerly the Quality Assurance Branch, to ascertain whether radioactivity measurements made by AQC are traceable to NBS. These

studies use radioactive reference test samples, with known but

undisclosed values, that are sent to AQC by NBS, and radioactivity

standards prepared by AQC and sent to NBS for confirmatory measurements.

Technical personnel of EPA and NBS decided, at a December meeting in

Washington, that in the future there will be more emphasis on the

checking by NBS of radioactivity standards calibrated and distributed

by EPA-LV. The criteria for conducting the studies are given in an appendix to the NBS-EPA interagency agreement of April 1976.

During the period of July 1979 through December 1979, NBS

provided AQC with seven solution reference samples and received

four results from AQC, which are listed in Table 9. Copies

of the Reports of Traceability Measurements are attached as Appendices 2 through 5.

52
TABLE 9

Reference Samples with Known, but Undisclosed, Values Provided to EPA-LV by NBS , July through December, 1979

Parent Radionuclides Month Sent

Mixed radionuclides July

Phosphorous-32 November

Scan d ium- 4 6 December

Tin-113 July

Iodine-131 July

Promethium- 14

7

October

Bismuth-207 . Au gu s t

Results Reported by EPA-LV to MBS, July through December, 1979

Parent Radionuclide AQC/NBS

Cobalt-58 0.961

Cerium-141 1.080

Lead-203 1.17

Plutonium-238 l.COO

53
rORM NBS-443

(REV. U tS)

U.S. DEPARTMENT OP COMMERCE

NATIONAL BUREAU OF STANDARDS

WASHINGTON, D.C. 20234

Appendix 1

REPORT OF CALIBRATION

FLY ASH FROM COAL COMBUSTION

FOR ASSAYS OF RADIUM-226 AND RADIUM-228

This sample consists of approximately 100 grams of fly ash, from the combustion

of eastern United States coal, in a screw-cap glass jar. The sample is from a batch of fly ash that had been passed through a 170-mesh sieve (90-um openings)

and then mixed for two hours. The tests for homogeneity are described in the

Supplemental Information section of this Report.

The radioactivity concentration of radiufn-226 per unit mass of fly ash in May

1979 was

*0.130 s-V1 ± 6 .

6

%*

.

Five weighed samples of the fly ash from one 100-g sample were assayed for

radium-226 by radi ochemi cal ly separating radium, removing the radon-222 from the

radium solution, and measuring the alpha-particle-emission rate of the radon and

its short-lived progeny in the NBS radon pulse-ionization chambers. In order to

confirm this result, the emission rates of gamma-rays from the decay of lead-214

and bismuth-214 were measured with a calibrated Ge(Li )-detector spectrometer.

The radioactivity concentration of radium-226 thus derived agreed with the cer- tified value to within three percent. Details of the assay methods are given in

the Supplemental Information section.

The uncertainty in the radium-226 radioactivity concentration, 6.6%, is the

linear sum of 1.1 percent, which is the limit of the random error of the pulsei oni zati on-chamber measurements at the 99-percent confidence level (4.604 Sm , where Sm is the standard error computed from a total of 22 measurements of five

samples), and 5.5 percent, which is the linear sum of the estimated limits of

conceivable systematic errors , including 3 percent for inhomogeneity, and 1.0

percent in the efficiency calibration of the pulse-ionization chambers. The

stated uncertainty is for a sample size of 10 grams or greater.

The radi oacti vi ty concentration of radium-228 per unit mass of fly ash in May

1979 was

*9.5 x 10- 2 s'V 1 ± 1 4%*

.

54
Twelve weighed samples of the fly ash were assayed for radium- 228 by measuring

the emission rates of gamma rays from the decay of radium-228 progeny, which

were in radioactive equilibrium with radium-228, using a Ge(Li )-detector spectrometer. The detector was calibrated using a weighed fly-ash sample that had

been quantitatively spiked with a calibrated gamma- ray-emi tti ng solution. Details of the assay method are given in the Supplemental Information section.

The uncertainty in the radium-228 radioactivity concentration, 14 percent, is

the linear sum of 1.6 percent, which is the statistical uncertainty in the

Ge ( Li )-detector measurements (three times the standard error of the weighted

mean), and 12 .

i

percent, which is the linear sum of the estimated limits of

conceivable systematic errors. Estimated limits of systematic errors include

3 percent for inhomogeneity, 4.5 percent for uncertainties in the values of

the gamma-ray-probabi li ties per decay, and 4.5 percent in the efficiency calibration curve for the Ge(Li) detector. The stated uncertainty is for a sample

size of 10 grams or greater.

The radioactivity concentration of radium-228 derived from measurements of emission rates of gamma rays from the decay of actinium-228 differs by only three

percent from the radioactivity concentration of radium-228 derived from measurements of emission rates of gamma rays from the decay of bismuth-212 and thallium208. Thus thorium-228 is, within the limits of the experimental uncertainty, in

radioactive equilibrium with radium-228 in the fly ash.

In September, 1978, 13 samples of fly ash were assayed for radium-228 using a Ge(Li )-detector spectrometer, and a value for the radioactivity concentration

was obtained that differed by only three percent from the certified value. Thus

radium-228 is, within the limits of the experimental uncertainty, in radioactive

equilibrium with thorium-232, and, analogously, radium-226 is probably in equilibrium with thorium-230. Because these two thorium isotopes have ver7 long half

lives, no decay corrections to the certified radium values will be necessary.

Prior to the weighing of working quantities of this material, they should be

dried in air at 40 °C for at least 24 hours.

When measuring emission rates of gamma rays from the decay of lead-214 and

bismuth-214, the sample should be in a closed, air-tight container for at least

a month prior to the assay, to ensure radioactive equilibrium with radium-226.

When measuring emission rates of gamma rays from the decay of lead-212, bismuth-212, and thallium-208, the sample should be in a closed, air-tight container

for at least four days prior to the assay, to ensure radioactive equilibrium with

radi urn- 224.

For the Director,

W. B. Mann , Chief

Radioactivity Section

Center for Radiation Research

duly 1979

55
SUPPLEMENTAL INFORMATION

Testing for Homogeneity

The fly ash was provided through the courtesy of the NBS Office of Standard

Reference Materials. From the 220 100-qram samples that were prepared, ten

percent were randomly selected and checked for homogeneity of gamma-rayemitting nuclides. These 22 samples were weighed into specially designed,

glass jars with plate glass bottoms and ground glass stoppers. The jars

were tapped until the samples occupied approximately equal volumes with a bulk

density of 1.1 g cm~3 t and the stoppers were sealed with wax. Each sample was counted for 10,000 seconds, live time, in a well -type Mai ( T 1 )-detector spectrometer. The gamma-ray-emi ssion rates from each sample were compared, using

pulse-height analysis, over five discrete energy regions containing the larger

photopeaks, and also over one region which comprised most of the gamma-ray

spectrum. No sample gave outlying results, based on a criterion discussed

by Natrella (1), using 0.05 as the value for alpha.

In order to check the homogeneity within a 100-gram sample, one was divided

into ten accurately weighed samples of about 10 grams each in plastic vials.

Each of these 10-gram samples was counted for 20,000 seconds, live time, in

a well-type Nal (T1 )-detector spectrometer. The gamma-ray-emission rates were compared as before except that six, rather than five, discrete energy regions

were used. Again, there were no outlying results, based on the same criterion.

The sample-to-sample inhomogeneity, for each energy region, was defined as the

range of the measured gamma-ray-emission rates for all the examined samples of

a particular size, minus the range of the measured gamma-ray-emi ssi on rates

from an equal number of repetitive measurements on a single sample of that

size. The sample-to-sample inhomogeneity in any of the energy regions, expressed

as a percent of the mean of the gamma-ray-emission rates for all the samples

tested of a given size, was no more than 3.] percent for either the 100-gram

samples or the 10-gram samples.

Assay for Radium-226

The fly-ash sample that had been divided into 10-gram samples for homogeneity

testinq was chosen to be radi ochemical ly assayed for radium-226. Accurately

weighed samples of about five grams each were processed by a procedure described in EML-300 (2). After processing each sample, its chemical yield was measured by counting the barium-133 tracer in the solution, using a well-type

Nal (T1 )-detector spectrometer. The amount of tracer initially added to each

sample was chosen to provide a gamma-ray count rate after processing of between

60 and 90 per second under the 356-keV photopeak of cesium-133.

Following the determination of the chemical yield, the sample was transferred

to a radon bubbler, and a few drops of 1-octanol were added to prevent foaming

during de-emanation. The sample was de-emanated, and radon was allowed to

collect for a period of 10 to 18 days. The solution was then again de-emanated,

56
and this radon was transferred by nitrogen, which had been bottled for at least

a month, through a gas-handling system into an MBS pulse-ionization chamber,

as described by Harding et ali a (3). Four chambers were used, each of which

was calibrated three times with an MBS radium-226 solution standard (Standard

Reference Material 4953). Each sample was counted one or more times in at

least three different chambers.

Each determination consisted of a series of consecutive 1000-second counts

over a period of one to several days. This series was started after polonium-214

was observed to have reached radioactive equilibrium with radon-222 in the pulseionization chamber. The same procedure was followed when measuring the chamber

backgrounds, using pure nitrogen. Each net sample count was corrected for the

decay of radon-222 that occurred during the time of collection and counting, using

a half life of 3.824 days. The radium-226 activity per gram of fly ash was then

calcul ated, wi th corrections for the chemical yield and the radium content of the

chemical reagents. The total radium-226 content in the quantities of the reagents

used to process a 5-gram sample of fly ash (the reagent blank) was assayed in the same manner as the fly-ash samples. The mean value from six assays was used as the

correcti on.

A confirmatory measurement for radium-226 was made in the manner described

below for radium-228. The following gamma-ray photopeaks were used for these

radium-226 assays: 295 and 352 keV from the decay of lead-214; and 609, 768,

1120, 1238, and 1765 keV from the decay of bismuth-214.

Assay for Radi um-228

Twelve of the 100-gram samples of fly ash that had been tested for homogeneity

were assayed by gamma-ray spectrometry for radium-228. The jars had been sealed

for at least a month so that radium-226 could be assayed at the same time, using

its gamma-ray-emitting progeny. The gamma-ray-emission rates were measured with

each jar sitting on a 65-cm^ Ge(Li )-detector spectrometer inside a mercury-fi 1 led

shield for 64,000 seconds, elapsed time, and the gamma-ray spectra were stored

on magnetic tape. A pulse generator was used to determine the dead-time correction.

Background spectra, of a jar filled with an equal volume of distilled water, were similarly accumulated.

Prior to the final data analysis, the spectra from each set were summed. The

locations and areas of the gamma-ray photopeaks, for samples and for backgrounds,

were determined by a computer program (4). Radionuclides were identified and net

count rates calculated.

The radioactivity concentrations of several progeny of radium-228 were computed

using gamma-ray-emission probabilities per decay that were compiled by Kocher (5),

and a Ge(Li )-detector-effi ci ency curve derived from a weighed 100-gram sample of

fly ash that had been quantitatively spiked with an NBS-calibrated solution con- taining nine gamma-ray-emitting nuclides. The spiking procedure, which was based

on work by Sill and Hindman (6), was carried out in a glove bag. The spiked

material was found to be homogeneous by measurements with a Nal (T1 )-detector

spectrometer of the gamma-ray-emission rates from accurately weighed samples of

about 10 grams each. When used to determine the Ge(Li )-detector efficiency, the

57
spiked samples were measured in the same counting geometry as were the unspiked

samples.

The reported radioactivity concentration of radium-228 is the weighted mean of radioactivity concentrations derived from these photopeaks: 463, 795, 911,

and 969 keV from the decay of actinium-228; 727 keV from the decay of bismuth-212;

and 583 and 860 keV from the decay of thallium-208. The weights were the reciprocals of the variances of the net count rates. A value of 0.3593 was used for the

alpha-particle branching ratio in the decay of bismuth-212 (5).

REFERENCES

(1) M. G. Natrella, Experimental Statistics , Par. 17.3.1.4, NBS Handbook 91,

National Bureau of Standards , Washington (1963).

(2) EML-300 , "Radiochemical Determination of Radium-226", procedure E-Ra-07

in EML Procedures Manual . USDOE Report EML-300, J. H. Harley, ed. , U.S.

Department of Energy, Environmental Measurements Laboratory, New York

(1978 revision).

(3) J. E. Harding, A. Schwebel and L. L. Stockmann, "Report on the Determination of Small Amounts of Radium in Solution", J. Assoc. Official Agricultural Chemi sts , £L li) , 311 (1958).

(4) F. J. Schima, D. D. Hoppes and A. T. Hirshfeld, "An Accurate On-Line

Method for the Evaluation of Peak Areas in Pulse-Height-Analyzer Data",

proceedings of a symposium Computers in Activation Analysis and Gamma-Ray

Spectroscopy, Mayaguez, Puerto Rico, April 30 - May 3, 1978 (in press).

(5) D, C. Kocher, "Nuclear Decay Data for Radionuclides Occurring in Routine

Releases from Nuclear Fuel Cycle Facilities", 0RNL/NUREG/TM-102 , Oak Ridge

National Laboratory (1977).

(6) C. W. Sill and F. D. Hindman, "Preparation and Testing of Standard Soils

Containing Known Quantities of Radionuclides", Anal. Chem. JL6., 113 (1974).

58
l\S. Depart mini of Commerce

Juanita Krep*

C" .'rcUfy

National C^rrau r/ Slamtard* Em«>i Arr.blrf. Dim to# Appendix 2

Report of Traceability Measurement by

QUALITY ASSURANCE BRANCH

U.S. ENVIRONMENTAL PROTECTION AGENCY

LAS VEGAS, NEVADA

on an NBS Reference Sample of Undisclosed Value of

This is to report that on the basis of nine measurements with a Ge (Li )-detector

spectrometer of the emission rate of the 811-keV gamma ray from the decay of

cobalt-58 in a solution reference sample of known, but undisclosed, total radioactivity, at 0700 EST September!, 1978, of

at 0700 EST September 1, 1978.

The QAB value differs from the NBS value by 3.9 percent. This result demonstrates

traceability of QAB to NBS for this measurement to within five percent, as specified in the appendix, "Traceability Studies", of the EPA-NBS interagency

agreement of April 20, 1976.

Supplemental information about this reference sample is on the attached sheet.

COBALT-58

*1.343 x 106 s" 1 ± 2.9%*,

the Quality Assurance Branch (QAB) reported a value of

1.29 x 10 6 s' 1 ± 5.5%

+ho ni K'ortni"

W.B. Mann, Principal Scientist

Radioactivity laboratory

Center for Radiation Research

September 17, 1979

59

*
SUPPLEMENTAL INFORMATION

for

COBALT-5 8 REFERENCE SAMPLE

of

SEPTEMBER 18 Y

8

The reference sample consisted of cobalt-08 in 0.21380 grains of carrier solution

in a fl ame-seal ed borosilicate-glass ampoule. The solution contained 00 micrograms of stable cobalt per gram of 4 molar hydrochloric acid, and was a quantitative dilution of a master solution, the radioactivity concentration of which

was measured relative to a radium- 226 reference source in the Nidi " ir "

y

pressure'

ionization chamber. The ionization chamber had previously been calibrated using

cobalt-58 solutions that were calibrated by Mai (II) counting.

The material from which the master solution was prepared was examined for photonemitting impurities with a Ge(Li )-detector spectrometer, and only cobalt-57 and

cobalt-60 were found. As of September 1, 19/8 the ratios of the activity of each

impurity nuclioe to that of cobalt-58, found by NBS and QAB, were:

IMPURITY NBS QAJf

cobalt-57 8.9 x 10' 3 ± 20 • 8.1 x 10' 3

cobalt-60 5.2 x 10~ 3 ± 20% 4.9 x 10" 3

.

The detection limits for impurity photons can be: expressed as a percentage of the

emission rate of the 811-keV gamma ra.y emitted in the decay of cobalt-58. These

limits for NBS are 0.1 percent for gamma rays with energies greater than 90 keV

and less than 806 keV, and 0.01 percent for those with energies between 816 and

1900 keV, provided that the impurity photons are separated in energy by 5 keV or more from photons of equal or greater intensity emitted in the decay of cobalt- 58.

A half life of 70.80 ± 0.08 days [NCRP Report. Mo. 58, Appendix A, National

Council on Radiation Protection and Measurements, Washington, 1978] was used to

calculate the NBS value for the cobalt-58 radioactivity of the reference sample

at the time of measurement by QAB. The total uncertainty in the NBS value, 2.9

percent, is the linear sum of the uncertainty in the radioactivity concentration

value of the master solution (2.7 percent), the uncertainty in the decay correction

(0,1 percent), and the systematic error associated with the dilution (0.1 percent).

60
I'.S. Depart r.*»t <>t Commerce

Juanita M. Krtpt

Secretary

National Standard. SmM.1 Air.Slrr. Direcli* Appendix 3

Report of Traceability Measurement by

QUALITY ASSURANCE BRANCH

U.S. ENVIRONMENTAL PROTECTION AGENCY

LAS VEGAS, NEVADA

on an NBS Reference Sample of Undisclosed Value of

This is to report that on the basis of 18 measurements with a Ge (Li )-detector

spectrometer on nine sources prepared from a solution of cerium-141 with a known, but undisclosed, radioactivity concentration at 0700 EST August 25, 1978,

of

at 0700 EST August 25, 1978.

The QAB value differs from the NBS value by 8.0 percent. The result demonstrates

traceability of QAB to NBS for this measurement to within eight percent, but does

not lie within five percent of the NBS value as specified in the appendix, "Traceability Studies", of the EPA-NBS interagency agreement of April 20, 1976.

Supplemental Information about this cerium-141 reference sample is provided on the attached sheet.

CERIUM-141

—*6.61 1 x 10 5 s'V1 ± 2.5%*,

the Quality Assurance Branch (QAB) reported a value of

7.14 x 10 5 s -1

g

_1 ± 3.4%

For the Director,

W. B. Mann, Chief

Radioactivity Section

Center for Radiation Research

August 6, 1979

61
SUPPLEMENTAL INFORMATION

for

CERIUM-141 REFERENCE SAMPLE

This reference sample consisted of cerium-141 in 5.327 grams of carrier solution

in a flame-sealed borosi 1 icate-glass ampoule. The carrier solution contained 66

micrograms of stable cerium per gram of 4 molar hydrochloric acid.

The radioactivity concentration of the master solution from which the reference

sample was prepared was measured, relative to a radium-226 reference source, in

the NBS "4tt"y pressure ionization chamber. The ionization chamber had previously

been calibrated, in terms of a radium-226 reference source, with cerium- 141 solutions which had been calibrated by 47rB-y coincidence counting.

The material from which the master solution was prepared was examined for photonemitting impurities with germanium spectrometer systems, and only cerium-135 was found. On August 25, 1978, the ratio of the radioactivity concentration of

cerium-139 to that of cerium-141 was 0.0065 ± 5%.

The detection limits for impurity photons can be expressed as a percentage of the

emission rate of the 145-keV gamma ray emitted in the decay of cerium-141. These

limits are 0.1 percent for gamma rays with energies greater than 20 keV and less

than 140 keV, and 0.01 percent for those with energies between 150 and 1900 keV,

provided that the impurity photons are separated in energy by 5 keV or more from

photons of equal or greater intensity emitted in the decay of cerium-141.

A half-life value of 32.501 ± 0.005 days was used for the decay correction (NCRP

Report No. 58, Appendix A, National Council on Radiation Protection and Measurements,

Washington, 1978).

62
1' S. Drpsrtment of Commerce

Juanita M. Krep*

oe.-rcl«y

Njlii nal BumiJ of Standard, Emoi Ambler. Dirnliw Appendix 4

^Mafional £Jnmm ni Jlfsitdards

Report of Traceability Measurement by

QUALITY ASSURANCE BRANCH

U.S. ENVIRONMENTAL PROTECTION AGENCY

LAS VEGAS, NEVADA

on an NBS Reference Sample of Undisclosed Value of

LEAD-203

This is to report that on the basis of 20 measurements v/ith a Ge(Li )-detector

spectrometer of the emission rate of the 279-keV gamma ray from the decay of

lead-203 in a solution reference sample v/ith a known, but undisclosed, total

radioactivity at 0700 EST November 22, 1978, of

*2.348 x 106 s* 1 ± 2.20%*,

the Quality Assurance Branch (QAB) reported a value of

2.75 x 10s s’ 1 ± 5.3%

at 0700 EST November 22, 1978.

The QAB value differs from the NBS value by 17 percent, and does not lie within

five percent of the NBS value as specified in the appendix, "Traceability Studies",

of the EPA-NBS interagency agreement of April 20, 1976.

The reference sample was ampoule number 16 of NBS Standard Reference Material

4420L, the certificate for which is attached. A half life of 52.05 ± 0.10

hours was used in the decay correction from the time of calibration to the time

of measurement by QAB (NCRP Report No. 58, "A Handbook of Radioactivity Measurements Procedures", appendix A, National Council on Radiation Protection and

Measurements, Washington, 1978).

The uncertainty in the NBS value of the total activity of the reference sample,

2.20 percent, is the linear sum of the uncertainty in the radioactivity concentration of SRM 4420L (1.67 percent), the uncertainty in the mass of solution in

the ampoule (0.05 percent), and the uncertainty in the decay correction (0.48

percent).

For the Director,

63 Radioactivity laboratory

September 17, 1979 Center for Radiation Research
L'.S. Department nl Commerce

•Juanita M. Krep>

8?“crtl:irv

tonal Bureau a! fiuiwUrd* t • If f C*6/ 4 it

^aitmtax mn ox ^hxnnnxu

(Eertiftcab

Standard Reference Material 4420L

Radioactivity Standard

Lead-203

This Standard Reference Material consists of lead-203 in s' e/3c grams of carrier

solution in a flame-sealed borosi 1 icate-gl ass ampoule. The solution contains

approximately 8 microqrams of lead per gram of approximately 0.5 molar hydrochloric

acid and has a density of 1.007 ± 0.002 grams per milliliter at 20.2°C.

The radioacti vity concentration of the lead-203 as of 1830 EST November 16, 1978,

was

*2.735 x 106 s'V1 ± 1.67%*.

This Standard Reference Material was measured, relative to a radium-226 reference

source, in the National Bureau of Standards "4tt"y pressure ionization chamber which

had previously been calibrated, in terms of a radium-226 reference source, with

lead-203 solutions from which quantitative sources had been prepared and 4ir(e,x)-Y

coincidence counted using the efficiency extrapolation method.

The solution from which this Standard Reference Material was prepared was examined

for photon-emitting impurities with germanftim-spectrometer systems and thallium-200,

thallium-201 and lead-201 were found to be present. As of the certification time,

the ratios of the activity of each impurity nuclide to that of the principal radionucl ide were

thallium-200 3.3 x 10~!j ± 60%

thallium-201 2 x 10"': ± 60%

lead-201 5.0 x 10" 4

± 20%.

The detection limits for impurity photons may be expressed as a percentage of the

gamma-ray-emission rate of the 279-keV gamma ray emitted in the decay of lead-203.

These limits are 0.1 percent for gamma rays with energies greater than 90 keV and

less than 279 keV, and 0.01 percent for those between 284 and 1900 keV, provided

that the impurity photons are separated in energy by 5 keV or more from photons of

equal or greater intensity emitted in the decay of lead-203.

The uncertainty in the radioactivity concentration, 1.67 percent, is the linear sum

of 0.02 percent, which is the limit of the random error at the 99-percent confidence

level (2.898 S m, where S m

is the standard error of the mean computed from independent

measurements of 18 samples) and 1.65 percent, which is the estimated upper limit of

conceivable systematic errors.

This Standard Reference Material was prepared in the Center for Radiation Research,

Nuclear Radiation Division, Radioactivity Section, W. B. Mann, Chief.

Washington, O.C. 20234 J. Raul Cali, Chief

December, 1978 64 Office of Standard Reference Materials

‘ SRM 44201.-..-
U.S. Department of Commerce JuamlA .M, Krep»

Secretary.'

National Burma of Standards

Ernest ^ rr.b'.rr. Uacctor Appendix 5

^National pureau of Jiiattdarrb

Report of Traceability Measurement by

QUALITY ASSURANCE BRANCH

U.S. ENVIRONMENTAL PROTECTION AGENCY

LAS VEGAS, NEVADA

on an NBS Reference Sample of Undisclosed Value of

PLUTONIUM-238

This is to report that on the basis of 20 measurements with 1 rr and 4tt proportional counters on a point source of plutonium-238 with a known, but un- disclosed, radioactivity on March 9, 1979, of

*385.0 s~\ ± 1.5%*,

the Quality Assurance Branch (QAB) reported a value of

385 s' 1 ± 2.8%

on March 9, 1979. The random component of the reported QAB uncertainty, 1.1

percent, is the standard error of the mean at the 99-percent confidence level.

The estimated upper limits of conceivable systematic errors were linearly

added to the random component.

The QAB value does not differ from the NBS value. This result demonstrates

traceability of QAB to NBS for this measurement to within five percent as specified in the appendix "Traceability Studies" of the NBS-EPA interagency

agreement of April, 1976.

This reference sample is Standard Reference Material 4906-B-4, the certificate

for which is attached.

For the Director,

fa^

/fe***^

W. B. Mann, Principal Scientist

Radioactivity Group

Center for Radiation Research

January 7, 1980

Attachment 65
U S. Department n[ Commerce

Junnita ,*?. Kre;s

Secretary

Netumsl Rurenw o( Steirinrde

fc.rn.ir Amk/.er, Durctor

(jleritftcai'e

Standard Reference Material 480S-B

Alpha-Particle Standard

Plutonium-238

This Standard Reference Material consists of a practically weightless source of

plutoni urn-238 electroplated onto a 0.010-cm-thick platinum foil 0.6 cm in diameter, which is cemented to a monel disk 2.54 cm in diameter and 0.16-cm thick.

The activity of the plutonium-238 at 1200 EST, July 1, 1978, was

This Standard Reference Material was calibrated in the National Bureau of Standards

"0.8tt"cx counter, which has an accurately known geometry.

The uncertainty in the activity, 1.5 percent, is the linear sum of 0.9 percent,

which is the limit of the random error at the 99-percent confidence level (3.499

where S m

is the standard error computed from eight measurements), and 0.6 percent,"

which is the sum of the estimated upper limits of conceivable systematic errors.

The solution from which this Standard Reference Material was prepared was examined

for gamma-ray-emitting impurities with a germanium-spectrometer system and gamma

rays with an energy of 59.6 keV were observed. If one assumes that the 59.6-keV

gamma rays are produced in the electron-capture decay of plutonium-237 impurity

atoms, the ratio of the activity of plutonium-237 to that of plutonium- 233 on August

8, 1977, was 7 x 10 . No other gamma-ray-emi tting impurities were found. It is

estimated that any photons between 20 and 400 keV would have been detected if their

emission rate were greater than 0.1 percent that of the 44-keV photons from the decay of plutonium-238 and were different in energy by at least 5 keV from any photons

emitted in the decay of plutonium-238.

A source made from the material was examined for alpha-particle-emitting impurities

with a silicon surface-barrier detector and none were observed. It is estimated

that alpha particles from impurity radionuclides would be detected if the emission

rate were greater than 10~ 4 of the plutonium-238 alpha-parti cl e-emission rate. The

alpha-particle-energy resolution of the silicon surface-barrier detector used in

the impurity measurement is 25 keV.

A half life of 87.74 i 0.04 years is suggested. +

This Standard Reference Material was prepared and calibrated in the Center for

Radiation Research, Nuclear Radiation Division, Radioactivity Section, W. B. Mann,

Chief.

Washington, D.C. 20234 J. Paul Cali, Chief

July, 1978 Office of Standard Reference Materials

66

SRM 4906-B-

+ Diamond H., Bent.ley W.C., Jaffey A.H. and Flynn K.F., Phys. Rev. C 15, 1034 (1977).

* 3. ?}/ /./O s"

1 + 1.53,*.
NBS-114A (REV. o-76 )

U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET

1. PUBLICATION OR REPORT NO. $ Recipient's Accession No.

4. TITLE AND SUBTITLE

NBS/EPA Energy Environment Project Semi-Annual Report

5. Publication Date

^ Performing Organization Code

7. AUTHOR(S)

C. C. Gravatt

8. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, DC 20234

11. Contract/Grant No.

12. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street, city, state, ZIP)

U. S. Environmental Protection Agency

Office of Energy, Minerals, and Industry

Washington, DC 20460

13. Type of Report & Period Covered

** - " '•

• - - - 15. SUPPLEMENTARY NOTES

I I Document describes a computer program; SF-185, FIPS Software Summary, is attached.

IS. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant bibliography or

literature survey, mention it here,) This semi-annual report describes the progress during the period July - December 1979 on the work performed by the National Bureau of Standards under an interagency agreement between the U. S. Environmental Protection Agency and the

National Bureau of Standards. The report ' consists of specific subagreements dealing

with the development of standards for the measurement of pollutants associated

with energy production and use.

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the tirat letter of the first key word unless a proper name;

separated by semicolons)

Air; Coal; Energy; Gases; Instrumentation; Monitoring; Particulates; Petroleum;

Pollution; Quality Assurance; Radiological Pollutant; SRM’s; Sulfur; Water

18. AVAILABILITY [ ( Unlimited

I I For Official Distribution. Do Hot Release to NTIS

I~1 Order From Sup. of Doc., U.S. Government Printing Office, Washington, DC

20402, SD Stock No. SN003-003- n Order From National Technical Information Service (NTIS), Springfield,

VA. 22161

19. SECURITY CLASS

(THIS REPORT)

UNCLASSIFIED

20. SECURITY CLASS

(THIS PAGE)

UNCLASSIFIED

21. NO. OF

PRINTED PAGES

22. Price

USCOMM-DC