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EPA-IAG-D8-E634

NB5/EPA ENERGY ENVIRONMENT PROJECT

SEMI-ANNUAL REPORT

TO

ENVIRONMENTAL PROTECTION AGENCY

OFFICE OF ENERGY, MINERALS, AND INDUSTRY

WASHINGTON, D. C. 20460

JULY 1979

U. S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS —QC

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EPA- IAG-D8 -E684

NBS/EPA ENERGY ENVIRONMENT PROJECT

SEMI-ANNUAL REPORT

TO

ENVIRONMENTAL PROTECTION AGENCY

OFFICE OF ENERGY, MINERALS, AND INDUSTRY

WASHINGTON, D. C. 20460

'JULY 1979

U. S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS

WASHINGTON, D. C. 20234

Page 10, l.a. Should read "Raman Microprobe Characterization

of Trace Polynuclear Aromatic Hydrocarbons

Page 25 Delete title

Page 30, 1 .d. Should read SRM 1643a.

TABLE OF CONTENTS

Page

FOREWORD^ ii

INTRODUCTION AND SUMMARY iii

8 0 - BC Ka - ENERGY RELATED POLLUTANT MEASUREMENT AND

INSTRUMENTATION DEVELOPMENT

1 Energy-Related Water Pollutant Analyses

Instrumentation 1

l.a Development of Marker Compounds 1

1 . b Application of Selective Detectors to Liquid

Chromatography 1

l.c Liquid Chromatography-Mass Spectrometry 2

1 . d Feasibility Study of Application of Particulate

Analysis by Ion Microprobe 5

1 . e Liquid Chromatography with Electrochemical

Detection of Organometallic Compounds . T5Q

l.f Laser Enhanced Ionization

80 -BC Kb -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 10

1 . b Development of Specific Immunoassays for

Dinitrophenols in Water 11

l.c LC-MS 13

l.d LC-EC 13
Page

1 . e Ion-Probe . . . . 13

1 . f Generation of Enhanced CARS Spectra of Organic

Liquids in Capillary Waveguides 13

80-BCLa-ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1

1 . a

l.b

1 . c

l.d

2

Development of SRMs for Stationary Sources

Associated with Energy Production 15

N0

2 in Air Gas Blend SRMs

SO

2 in Air SRMs

NO in N

2 SRMs

0 ? in N ? SRMs

Development of SRMs for the Monitoring of Ambient

Air Impacted by Emissions Resulting from Energy

Production

15

16

16

16

16

2. a Trace Level Reactive Gas SRMs 16

2.b C0 ? in Air 16

2.c Automation of Gas Analysis 17

2 . d . Development of a Traceability Procedure for Gas

Standards 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 18

4 Particulate Physical and Chemical Characterization . . 18

4 . a . Particle Doppler Shift Spectrometer (PDSS) 18

4.b. Nonspherical Particles IP

4.d.e Development of Air Supported Plasmas 20

5 Particulates on Glass Fiber Filters 21
Page

6 Urban Air Particulate Washington D. C. Sample .... 22

7 Develop SRMs for Coal Conversion Processes and

Materials Balance Determinations 23

8 Development of an Oil Shale SRM 24

80 -BCLb -ENERGY RELATED AIR POLLUTANT ANALYSIS INSTRUMENTATION

1 Development of an Instrument to Measure Airborne

Sulfate Particulate Matter . ] ! ^ ! ] ! !! ! ! ! . . . 26

80 -BCLc -ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 Radiocarbon as an Environmental Tracer 28

80 -BCMa- ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 Energy Related Water Pollutant Standard Reference

Materials 29

l.a Complete Certification of Ocean Sediment SRM 29

l.b. Estuarine Sediment, Proposed SRM 1646 29

l.c Anions in Water SRM 29

l.d Trace Elements in Water SRM 29

1.

e The Role of Internal Standardization in Analysis

of Aqueous Samples Using the Inductively Coupled

Plasma (ICP) Technique . . ! ] ! I 1 ! T"-

! ! . ! . . . 29

2 SRMs for Organic Analysis 33

2 . a/b Production of an Aqueous PAH SRM 33

2.

c Inter laboratory Comparison Exercise 34

2 . d Spectroscopic Certification Technique for Analysis

of Trace Organics in Water SRM 34

80 -BCMb -ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 Develop Organic Standard Reference Materials for

the Calibration of Energy-Related Water Pollutant

Measurement Methods 39
80 -BCN- ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

Page

1 Radiological Pollutant Quality Assurance 44

l.a Solution of Plutonium- 241 46

l.b. Fly Ash from Coal Combustion. 46

l.c. Thorium-232 Solution 46

l.d Mixed Radionuclide Solutions. . 46

2 Measurement Traceability Studies with the Quality Assurance

Branch of EPA-LV

*
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

i 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 environemntal 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 Resarch

and Development Series

.

rinhi 111 m•

i C. C. Gravatt

Chief, Office of Environemntal Measurements

National Bureau of Standards

ii

i
INTRODUCTION AND SUMMARY

This report describes work performed by the National Bureau of Standards

(NBS) during the period, January 1979 to June 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 the measurement of pollutants

associated with energy production and use. The highlights for this

reporting period in the eight, subagreement areas are:

80 BCKa - ENERGY RELATED POLLUTANT MEASUREMENT AND INSTRUMENTATION

DEVELOPMENT

Under the task Energy- Related Water Pollutant Analysis Instrumentation for

Research and Ambient Characterization Studies, several refinements have been

incorporated into the liquid chromatography-mass spectrometry interface,

some practical operating experience was gained with the refined system

and scientists are developing plans to apply this system to analytical

problems

Studies of organic layers on particles by ion microprobe mass analysis

revealed that characteristic fragment ions as well as parent molecule

ions can be observed in spectra obtained from layered particles.

Development of the Master Analytical Scheme progressed sufficiently during

this reporting period so that three major NBS responsibilities were

defined.

Significant progress was made in the electrochemical detection of organometallic

compounds by optimizing detectors used in the system and improving the

separation of organo species in the liquid chromatography step.

A final report is being prepared on the laser- enhanced ionization work.

iii
80 BCKb - ENERGY RELATED WATER POLLUTANT ANALYSIS INSTRUMENTATION

Under the task Development of Measurement Methods for Non-Volatile Organic

Pollutants in Water Due to Energy Technologies work is being performed to

optimize the NBS-developed Raman microprobe for its application to the

analysis of small volumes of organic effluents.

Work is being performed on the development of specific immunoassays for

dinitrophenols in water. Considerable effort has been spent developing a technique to optimize a small molecule immunoassay using tritrated

dinitrophenol or a derivative thereof.

Wave guide coherent anti-Stokes Raman Spectrometry has been shown to be a sensitive and highly specific "detector" for trace organics when coupled

with chromatographic separation techniques.

80 BCLa - ENERGY RELATED POLLUTANT MEASUREMENT AND INSTRUMENTATION

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 procured for certification and preliminary homogeneity

analyses of the 250 and 500 ppm mixtures were completed; two new SRM’s

for NO in nitrogen at 15Q0. and 300.0 ppm were certified and are now

available; and analyses have been initiated for certification of 0? in

nitrogen at 2 and 10% 0

2

. Under Development of SRM’s for Monitoring of

Ambient Air Impacted by Emissions Resulting from Energy Production,

preliminary work for the preparation of C0

2 in air mixtures in the 100-

50Q ppm range indicated that a total C0

2

concentration uncertainty of +_ 0.1

relative may be achieveable; a second NBS Computer Operated Gas Analysis

System (COGAS) having up to a 30-cylinder capacity is being assembled;

and an NBS traceability procedure has been prepared for production of

gas standards ("Certified Reference Materials") by the compressed gas

suppliers that would provide traceability of commercial gases to NBS.

IV

o\°
In X-ray fluorescence particulate analysis, work continued on focus edion beam sputtering to produce thin glass films. Two additional glass targets

of different elemental compositions have been used for thin filter

preparation.

Under Particulate Physical and Chemical Composition, the internal calibration of

the Particle Doppler Shift Spectrometer was improved by a factor of four

for measurement of 5-18 ym aerosol, and prospects are promising to extend

the measurements down to 0.5 ym or less. In addition, numerical calculation

techniques have been developed for nonspherical particles, and the

capability now exists to calculate optical scattering properties of a variety of nonspherical particles as a function of particle shape, size,

and index of refraction. Further, work has progressed on evaluation of

an air-supported plasma torch, which, when coupled to a laboratory

spectrometer and recorder, can be used for direct monitoring of airborne

lead Cot mercury) , the net system of which is readily amenable to

minaturization as a portable instrument.

Glass fiber filter strips as candidate SRM’s containing nominal

concentrations of 100, 30.0, and 150Q yg of lead per strip were prepared

and analyzed by linear sweep voltammetry. Recoveries of lead from

these strips for analysis and the precision and accuracy of analysis were

all found to be excellent.

MBS SRM 1648, Urban Particulates, collected in the St. Louis area, has

been certified for a number of elements and was made available by the NBS

Office of Standard Reference Materials in March. Collection of urban air

particulate matter in the Washington, D. C. area has progressed well.

Preliminary analyses have been carried out on the Washington collection

for inorganic and organic components, and comparisons have been made to the

St. Louis material.

Under SRM development for coal conversion processes, Western Coal (SRM 1635) was found to contain about 18 times more low evaporation temperature sulfur than

Pennsylvania Coal (SRM 1632a) . Preliminary analyses were completed for

v
organic surface layers on single particles using a differential backscattering

system.

Under activities on oil shale, preliminary analyses were undertaken for

organics extracted from an homogenized oil shale using gas chromatography

and glass capillary columns.

80 BCLb— ENERGY RELATED AIR POLLUTANT ANALYSIS INSTRUMENTATION

A systematic study of the effects of SO

2

concentration and relative

humidity on response of the Particulate Sulfate Instrument found that

the flame photometric detector was sensitive to sample relative humidity

only below 10% and above 80%, and that SO

2

interferred with the particle sulfate

response only at very high SO

2

concentrations.

80 Bac- ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND ASSOCIATED

METHODS AND TECHNIQUES DEVELOPMENT

Work on the mini -radiocarbon low-level counting method and instrumentation,

focusing on the use of radiocarbon as an environmental tracer to discern

natural from anthropogenic carbon sources, demonstrated the validity of

the method in the field and served to underline the potential serious

impact of residential wood burning on fine carbonaceous air particulates

in urban areas.

80 BCMa - ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND ASSOCIATED

METHODS AND TECHNIQUES DEVELOPMENT

Under the Energy Related Water Pollutant Standards Reference Materials for

Conventional Fossil Technology task, the Trace Elements in Water SRM (1643a)

is in the final stages of certification and will soon become available.

There was no activity this reporting period on the ocean sediment SRM,

Estuarine Sediment SRM or on the Anion SRM.

vi
Work on the Inductively Coupled Plasma (ICP) technique focused on

isolation and optimization of non-random variability in the measurement

technique. Some progress has been made. Additionally, a continuum-source

Echelle wavelength modulation-atomic absorption spectrometer (CEWM-AA) is

being evaluated for the determination of trace metals in a wide

variety of samples.

In the area of SRM's for organic analysis, the procurement process for the

production of an aqueous PAH-SRM is still in progress- Additionally, NBS

is participating in an interlaboratory comparison exercise to both

validate NBS general methodology and check the effect of refinements to this

methodology.

A new measurement technique- -laser Raman scattering in isolated cryogenic

matrices--is being investigated for the analysis and certification of

priority pollutants in materials.

80 BCMb - ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

The work under this task is focused on the development of Standard

Reference Materials (SRM’s) for organic water pollutants associated with

emerging energy technologies. Current measurement methodology is not

adequate for the development of SRM's required to support effective monitoring

programs for advanced energy- related organic water pollutants. Thus, efforts

are closely related to BCKh elements.

80 BCN - ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND ASSOCIATED

METHODS AND TECHNIQUES DEVELOPMENT

The work in the Radiological Pollutant Quality Assurance task involved providing

measurement traceability, through the EPA/Las Vegas Laboratory, for certain

radionuclides not included in other programs. Efforts were focused on

vii
providing four materials to be used in a radiological pollutant quality

assurance program: Plutonium- 241 solution; thorium- 232 solution; fly ash

from coal combustion; and a mixed radionuclide solution.

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

AND DEVELOPMENT

1 . Energy-Related Water Pollutant Analysis Instrumentation

1 . a . Development of Marker Compounds

Development of the Master Analytical Scheme has progressed

sufficiently that the following NBS responsibilities have

been defined.

1) NBS will synthesize a deuterium labeled naphthalene sulfonic

acid and labeled disodiumdodecyl phosphate. If a synthetic

route cannot be found, NBS will report their research results by

the end of August 1979.

2) NBS will perform purity checks on the approximately forty

deuterated marker compounds to be supplied by Research Triangle

Institute and Gulf South Research Institute. These purity checks

will include checks for isotopic as well as chemical purity of

the marker compounds. The target date for supplying this information will be 30 days after receipt of the samples.

3) Once marker compound solutions for the Master Analytical

Scheme can be prepared, NBS will monitor stability of these

solutions for the duration of the Master Analytical Scheme

contract (i.e., through the end of phase three). Included in

the stability monitoring will be reactivity of the components in

the mixture and long-term losses of components of the mixture for

other reasons. The stability of these solutions will be monitored

both at refrigerator and at room temperatures

1 . b . Application of Selective Detectors to Liquid Chromatography

See section BCK-a-l.e.
1 . c Liquid Chromatography-Mass Spectrometry t

Several further refinements have been incorporated into the LC-MS

interface and some practical operating experience has been gained

during this reporting period. Heaters composed of Chromel wire

with bases cast of refractory cement were designed and fitted to

the ion source. The heaters make it possible to achieve source

temperatures of above 350 °C, if desired,, and to maintain the

source temperature while the filaments are off.

The probe was fitted with an improved heat sink which is vented

so as to prevent the interior of the heat sink from being a dead

volume connected to the ion source.

It was discovered that the probe valve configuration was not

giving a spray of liquid. Therefore the probe valve was changed

from

:

to

!
and finally to:

Tests showed that the latter configuration gave the desired spray

of liquid. A thermocouple device was constructed to measure the

temperature at the probe tip; the temperature appears to not

exceed 35 °C when in the desired position.

The mass spectrometer was tuned with perf luorotr ibutylamine , good

resolution being obtained. The detection limit of methyl

stearate on the solids probe was measured to be about 1 ng.

Two liquid chromatographic separations were monitored with the

mass psectrometer . A mixture of polynuclear aromatic hydrocarbons

( FAH) was eluted from an aminosilane column with i-octane containing 5 percent methylene chloride at a flow rate of 1 mL/min.

The elutent was passed through a UV detector, doe the concentrator

wire, and into the mass spectrometer. The peaks were about 30

seconds wide at the UV detector and were delayed about 1 minute

and broadened by about 15 seconds at the mass spectrometer. The

detection limit for phenanthrene , for example, was found to be

about 2 ng injected into the column. Without the use of the

concentrator wire, the detection limit was about 40 ng

A mixture of aromatic nitrogen compounds was examined, injecting

200 ng of each and eluting with i-octane containing up to 20

percent methylene chloride. It was found that, by varying the

flow rate of solution into the source, spectra of Chemical

Ionization or mixed Election Impact Chemical Ionization

character could be obtained.

3
A control device for the power input to the concentrator wire was

constructed. It operates on the principle of monitoring the drop

size at the bottom of the wire with a photocell feedback circuit

controlling the applied current. This allows us to approach very

nearly zero flow at the bottom of the wire without overheating

and depositing the solute on the wire. Approximate maximum LC

flow rates which can be accommodated are shown in Table 1.

Table 1

Solvent Max. Flow Rate, mL/min AHv ca

n-pentane 3.1 90

i-octane 2.8 90

methanol 1.7 280

50% Me0H/H

2

0 0.7 420

A limitation in the amount of concentration increase which can be

obtained is the loss by capillary migration of solution from the

junction of the concentrator wire and the point of entry into the

probe tube. Teflon FEP coatings and PTFE bushings have been

tried with only moderate success. A change in the geometry may

be necessary.

Further development of the power control of the concentrator will

eventually be necessary, as will the trial of several means to

prevent loss of solution from the junction of the concentrator

wire and the probe tube. Apart from the above, we are now at a point in the development of the LC/MS interface where we can

begin to apply it to analytical problems.

A patent application has been filed with the NBS legal advisor

and he has been in contact with the appropriate EPA counsel,

Mr. Ben Bochenek.

4
1 . d Feasibility Study of Application of Ion Microprobe

Particulate Analysis

The project on the investigation of organic layers on particles

by ion microprobe mass analysis has been initiated and work is

now in progress. We are currently studying known organic layers

deposited on metallic spheres. The initial studies have revealed

that characteristic fragment ions as well as parent molecule ions

can be observed in spectra obtained from layered particles in the

20-25 ym range. Additional studies will be carried out, and a final report on the project will be available in September 1979.

1 . e Liquid Chromatography with Electrochemical Detection of

Organometallic Compounds

Significant progress has been made in the electrochemical detection

of organometals and organic compounds separated by LC. The work

has been divided between detector optimization and species

separation.

Detector Optimization

Various electrode materials were evaluated for their use in

reductive electrochemical detection. Six electrodes including

the dropping and hanging mercury, gold amalgam, platinum amalgam,

glassy carbon and mercury coated glassy carbon electrodes were

compared for their potential ranges and detection limits for a reducible organic compound. A manuscript detailing this work has

been submitted to Analytical Chemistry.

Organotin Separation and Detection

Some of the trialkyl organotin cations have been separated by

reverse-phase chromatography using an organotin complexing

agent with dimethylsulfoxide (DMSO) . Organotins most frequently

behave as ’’hard” Lewis acids, and DMSO was chosen as a suitable

5
"hard" Lewis base. Together they form neutral complexes of the

type R-rSn(DMSO) (counter anion), where X can be 1 or 2 (1). The

neutral complexes are then separated by reverse -phase chromatography

(see Figure 1)

.

Xn\«cT ^ k *3 / o /x /V / c> /£> M

Figure 1

A cation exchange separation has been developed by Jewett et al

.

(2,3) for the trisubstituted organotin cations. This separation

was used for further evaluation of the electrochemical detection

approach, outlined in the following text.

Some difficulty has been encountered when constant potential

amperometry is employed for the detection of the organotin

cations. Figure 2A shows the amperometric detection of ^Sn"**

at a potential that produces a current on the limiting current

plateau. A positive reduction current due to the 4>^Sn

+ is

initially observed, followed by a significant dip in the residual

current baseline. This behavior can be explained by the electrochemical behavior of the trisubstituted org,anotin cations :

^-0.7 V

(j^Sn"*" + e ^ ^Sn* (ads) I slow

Z^^Sn*' (ads) ->• ^6^n

2 ^

6
The cj) 3

Sn

+ is initially reduced quasi reversibly to the (Jj^Snradical which is adsorbed at the electrode surface (4)

.

If a

constant potential is applied just above -0.7 V, sufficient (J^Sn*

is produced to dimerize (II). The 4>gSn

2 produced is highly

adsorbed at the electrode surface and is not further reducible

at this applied potential. The ^gSn^ covers the electroactive

surface of the electrode, which lowers the residual baseline

current (caused by the solvent), resulting in the observed dip.

This detection problem can be overcome by using a pulsed waveform

rather than holding the constant potential above -0.7 V. Figure

2B illustrates the approach, where a potential is applied which

does not cause (I) but periodically a more negative potential

pulse is applied which does initiate reaction I. The reduction

current is sampled at the end of the pulse, still giving a response proportional to the tp 7 Sn

+ concentration, but now the

duty cycle of the electrode is greatly reduced (to 10% in Figure

2B and C) . Therefore less cj^Sn* is generated. During the main

duration of the potential cycle the <j>?Sn* produced can also be

reoxidized to ct^Sn by the return to a more oxidizing potential.

The low duty cycle and reoxidation prevents the buildup of 4>^Sn^

and therefore eliminates the baseline dip. Even higher sensitivity can be obtained if the differential pulse mode of operation

is employed (shown in Figure 2C)

.

The differential pulse mode of detection was used for the measurement of very small amounts of two trialkyltin species shown in

Figure 3, by using a compromise detector potential and large

pulse height (potential window) . A somewhat better detection

limit could be obtained if the potential and pulse height were

optimized for each species.

Future work will involve development of a separation of the monoand disubs tituted tin species and an investigation into the water

stability of the dialkyltin cations.

7
U^'tc.otl 0 a -c.86 \/

Pu tse

Deied'tC'A

-0.657, /So*!/ p.Kt

O.S’ s puls€ pe^vod^

PrPflce^» «A Puis e.

-0.US7, /OOr+'JG*

0.5" S’ 0ujs«- p2.rtod

FIGURE 2 8
!

Figure 3

References

1. R. C. Poller, Chemistry of Organotin Compounds , Academic

Press , N. Y . , 1970

2. Speciation of Triorganotin Halides by HPLC-GFAA, K. L. Jewett,

F. E. Brinckman, and W. R. Blair, 186th ACS Natl. Mtg.

,

Washington, D. C., September 1979 (Analytical Div)

3. New Methods for Speciation of Bioactive Organotin Leachates

from Antifouling Paints and Polymers, K. L. Jewett,

W. R. Blair, and F. E. Brinckman, 6th International Symposium

on Controlled Release of Bioactive Materials, New Orleans,

LA, 6-8 August 1979.

4. S. G. Maironovskii , Russ. Chem. Rev. 4_5_, 298 (1976).

1 . f Laser Enhanced Ionization

A final report is being prepared on this activity.

9
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

Polynuclear Aromatic Hydrocarbons

Activities have recently been resumed in the project area.

The analytical goals and the status of this work as of two months

ago are described in a recently published paper (1)

It was demonstrated that micro-Raman spectroscopy (MRS)

offers high molecular/structural specificity and picogram sensitivity for PAHs of interest in environmental pollution studies.

Based on the results of feasibility experiments, it was proposed

that the MRS technique be developed as a potentially powerful,

new method for the detection and identification of trace level

organics separated by chromatographic procedures.

The work that has now been initiated aims at applying the

NBS -developed Raman microprobe to the analysis of isolated, small

volumes of the effluent from a liquid chromatograph. Because of

the design of the instrument (i.e., the illumination/co llect ion

geometry utilized in the fore-optical system) , it is necessary

that any desired fraction of the chromatographic effluent stream

be isolated and analyzed in a static mode. This requires that

fractions of the effluent be trapped and localized on a sample

support which does not interfere with the microprobe measurement.

Various schemes are being investigated for the collection and

localization of liquid chromatographic fractions. Isolation in

microscopically confined areas (or sampling volumes) of sapphire

substrates has particular advantages in that sapphire (a-A^O-)

presents only minimal spectral interferences by Raman (and

fluorescence) scattering (1) . A second approach isolates the

effluent by adsorption onto a fine particulate solid (e.g., alumina)

which can be analyzed in the microprobe by the usual techniques.

10
l.b . Development of Specific Immunoassays for Dinitrophenols

in Water

Work during the past six months has focused on the techniques

required to optimize a small molecule immunoassay using tritiated

dinitrophenol or the tritiated derivative. Dinitrophenol -Llysine, e- [phenyl 1,3,5- H(N)]. Charcoal and several types of

antibody-coated beads were used as separating agents.

Results obtained so far showed that only a small fraction of

the H -DNP-Lys is bound (ca. 1% or less at about 1 yg/mL of the

antigen) ; and the precision is still rather poor. It appears

that there are significant non-specific binding reactions and

that the affinity of the antibody for DNP-Lys is not as strong

and specific as we had hoped. We tried various procedures to

eliminate some of the sources of variability in the results and,

hopefully, to be able to still obtain an immunoassay for DNP with

the material currently available.

(a) Purification of the Antiserum by Affinity Column Chromatography

The majority of the albumin and non-antibody protein in the serum

is removed by use of DEAE cellulose (D52) columns and then by an

affinity column packed with affi-gel 102 reacted with EDNPlysine. The antibody fractions were dialyzed in an ultrafiltration cell and analyzed by means of cellulose acetate electrophoresis. The purified material showed only marginal improvement

over the antiserum specificity and affinity toward the EDNPlysine. Further work is indicated here since the antibody

appears to be very pure.

(b) Charcoal precipitation

Darco charcoal was used to precipitate out all unbound antigen

from the solution. Only the bound antigens are supposed to

11
remain in the solution phase. However, we found that in the

solutions without any antibody, a residual activity remains in

the solution after the charcoal precipitation. The magnitude of

this residual activity is of the same order as the activity in

the supernate when antibody is present. Thus the correction for

the background count is as large as the net count for bound

antigen. Increasing the charcoal to fourfold the normal amount

employed did not decrease this background count significantly.

Work indicates the need to use solid-phase beads coated with a second antibody as a means of separating the free from the bound

antigen

(c) Immunobeads

We had tried several of the commercially available beads, e.g.,

DASP, which is a sheep anti (rabbit immuno -globulin) immunosorbent,

and immunobeads of Bio-Rad, which are beads with rabbit IGG bound

to them. In these techniques, the bound DNP-lysine is precipitated

with the beads, therefore the activity of the precipitate is only

a small fraction (ca. 1%) of that in the supernate, because of

the low affinity of the antibody. The precipitates have to be

washed at least twice, with about 10-fold the volume of the

precipitate. However, excessive washing seems to increase the

variability of the results, probably due to either the loss of

beads or the shift in binding during washings. Due to the configuration of the polyethylene vials we normally used, the precipitates were not packed well, and the precision suffered because of

inclusion of supernate and loss of some of the beads during

washing and removing of the supernatants. We subsequently tried

a narrower glass tube with rounded bottom, and the reproducibility

of assay improved. However, the adsorption of the antigen onto

the surface of these tubes gives a background count comparable in

magnitude to the net count from the beads.

12
The low affinity and specificity of the available antibodies

seem to be limiting the development of a sensitive and accurate

RIA. Most of our results at present are qualitative. Preliminary

results indicate that competitive binding of non-radioactive DNPLys appears to lower the count of the bound radioactive DNP-Lys

in the precipitates. However, due to the large background count

at present, we are not able yet to quantitate the results to

obtain a standard curve. It appears that we might beneficially

spend some effort in obtaining an antibody which has stronger

affinity toward DNP, thus making the interferences and errors due

to the background relatively insignificant.

Other approaches will include the potential use of labeling the

antibodies with iodine-125 in an attempt to utilize the more

specific procedure of antibody labeling with a high specific

activity gamma emitter.

A variety of DNP-labeled compounds have been procured in the past

few months. These compounds are expected to show fluorescence

quenching and spectral shifts in the presence of specific antibody.

Work will be directed toward this phase of the project during

June and July, 1979.

l.c. LC-MS , Covered under Section 80 -BCK-a, 1 . c

.

l.d. LC-EC , Covered under Section 80 -BCK-a , 1 . e

.

l.e. Ion-Probe - Covered under Section 80 -BCK-a , 1 . d.

1 . f . Generation of Enhanced CARS Spectra of Organic Liquids in

Capillary Waveguides

NBS scientists have demonstrated the generation of coherent antiStokes Raman spectra (CARS) in a liquid filled optical wave guide.

This is the first demonstration of the ability of an optical wave

guide to produce, over a substantial portion of its total length,

13
frequency tunable, phase matched non-linear mixing in a dispersive medium.

Non-linear mixing in a dispersive medium requires fixed angular crossing of

the interacting beams (momentum conservation) , and thus , these results

demonstrate that the wave guide maintains the necessary angular relationships

over a substantial fraction of its length. The wave guide technique leads

to CARS signals 1-2 orders of magnitude stronger than those obtained by more

conventional CARS techniues. This signal enhancement is realized for samples

whose total volume is only a fraction of a microliter (total volume of the

wave guide is -0 . 75 yL) . In the wave guide, signal is generated from

virtually all this volume, which should be contrasted with conventional

methods which effectively utilize only a few hundred picoliters of a sample

whose total volume is tens of microliters (at minimum) . Wave guide CARS is

particularly significant for analyzing small volume such as the eluent from

a liquid chromatograph. A simple hollow quartz or Pyrex capillary, as used

in these experiments, is well suited for this application. CARS has been

shown to be a sensitive and highly specific "detector" for trace organic

analysis when coupled with chromatographic separation techniques.

The inherent efficiency of optical excitation within a wave guide, and

the enhanced sensitivity of vibrational spectroscopy by wave guide CARS

suggests this as a potentially important tool for studying excited state

dynamics in liquids.

Reference

[1J E. S. Etz , S. A. Wise, and K. F. J. Heinrich, "On the Analytical

Potential of Micro-Raman Spectroscopy in the Trace Characterization

of Polynuclear Aromatic Hydrocarbons," in Trace Organic Analysis : A New Frontier in Analytical Chemistry , Proc. 9th Materials Research

Symposium, NBS Special Publication 519, U. S. Government Printing

Office, Washington, DC (April 1979).

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

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 . Development of SRMs for Stationary Sources Associated With

Energy Production

l.a. NO

2 in Air Gas. Blend SRMs

The NC^-air mixtures at 250, 500, 1000 and 2500 ppm have all been

ordered in lots of 52 each. The 250 and 2500 ppm mixtures were

received in early June after a long delay due to technical difficulties encountered by the gas supplier. The 500 and 1000 ppm

mixtures are scheduled for delivery around mid- July.

The cylinders are expected to have a relatively wide range of

concentration within each batch when compared to other less reactive

gas mixtures prepared in the same manner. However, the stability

is expected to be satisfactory. Continuing analyses of 500 and

2500 ppm mixtures over the past 2 years have shown no essential

instability.

Three methods of analysis will be employed in the certification

of these materials as SRMs. The concentration of each sample in

a lot relative to all others in the lot will be determined by

chemiluminescence. The absolute value of a limited number of

samples will be determined by a chemical method, following an

accurate dilution of the sample, and by a gravimetric technique.

These two methods have been intercompared and were found to agree

to better than ± 1 % relative.

The analysis of these samples is considered of highest priority

because of the necessity for a second analysis at some later date

of at least a portion of each batch. This is considered essential

to establish the stability of the commercially-prepared samples.

15
l.b. SO-, in Air SRMs

No work was done during this reporting period due to lack of

funds for purchase of SRMs.

l.c. NO in N? SRMs

Two new SRMs have recently been developed and issued through the

NBS-MVMA Research Associate Program. These are SRM numbers 2630

and 2631 (1500 and 3000 ppm NO in N

2

, respectively).

l.d. 0 ? in N^ SRMs

Oxygen in N^ mixtures at 2 and 10% 0

2 have been ordered and delivery

is scheduled for mid-July. Appropriate standards have been prepared and the methods of analysis are perfected such that no

problems are anticipated with the analysis and certification of

these materials as SRMs.

1 . e . Stationary Source Gas SRMs

The final report on this phase of the program will be issued by

September 30, 1979.

2 . Development of SRMs for the Monitoring of Ambient Air

Impacted By Emissions Resulting from Energy Production

2 . a . Trace Level Reactive Gas SRMs

The preparation of samples S0

2

, N0

2 and NO in Air or N

2 at subppm levels as SRMs has been found intractable, and further work

will not be undertaken at this time.

2.b. C0

2 in Air

A gravimetric technique has been developed for the preparation of

16
gas mixtures in the range from 100 to 500 ppm. The method allows

direct preparation at these levels without the requirement of

intermediate steps. Preliminary results using C0

2

and air indicate

that a total uncertainty of less than ± 0.1% relative may be

readily achieved.

A comparison of several mixtures prepared by this method with

those of two other laboratories using different techniques has

shown very promising results. A more extensive program supported

in part by other agencies is planned to complete the investigation.

It is still anticipated that SRMs of C0

2 in air certified with a total error of no more than ± 0.3 ppm will be produced during 1980.

2 . c . Automation of Gas Analysis

Work is continuing to expand the capability of the NBS-developed

Computer Operated Gas Analysis System (COGAS) . However, rather

than expanding the capacity from 20 to 50 cylinders it was decided

to build a duplicate system having up to a 30 cylinder capacity.

It was felt that while another system would cost slightly more

than expanding the original system, the increased versatility

relative to SRM production would be considerably more cost-effective.

Parts for assembly of this second system have been ordered. In

addition, a system for automating the calibration of permeation

tubes is nearing the point where testing can begin.

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

The serious shortage of certain gas SRMs has been of great concern

to NBS for the past several years. Efforts are underway to increase

the number of samples restocked next year, but it is obvious that

such an increase will only serve to partially resolve the problem.

The continued demand for existing SRMs and the need to produce new

ones will continue to occupy a significant percentage of available

manpower and require a major portion of the funds available for

certification of SRMs.

17
Accordingly, a procedure has been developed by which the specialty

gas industry may produce gas mixtures of SRM quality. These

mixtures, tentatively called "Certified Reference Materials"

CRMs) , will be prepared according to a procedure developed by

NBS. Such mixtures will duplicate certain SRMs , and when properly

prepared will have total uncertainties slightly greater than the

uncertainty of the corresponding SRM. This procedure is currently

being reviewed by NBS and by several groups within EPA.

After these reviews are completed, the procedure will be reviewed

by representatives of the Compressed Gas Association in order that

a full understanding of the procedure and its implications will be

attained by those companies who wish to produce CRMs.

3 . Develop Methods for Dispersal of Particulates on Filter Media

and Methods for Determining and Controlling the Composition

and Morphology of Such Dispersed Particulates

Thin Glass Films Produced by Focused- ion Beam Sputtering

In our last semi-annual report (EPA- IAG- 08 -E684) of February 1979

we described our work on thin glass films produced by focused-ion

beam sputtering for calibration of x-ray fluorescence spectrometers.

We have recently fabricated two additional glass targets of different elemental composition for use in preparing thin films. One

of these consists of SiC^ , Na

2 SO^, and Ma 20 ; the other contains

A1 ? 0^ and Na^PO^. Experiments to produce thin foils containing

sulfur and phosphorous from these glass targets are now in progress

and will be reported in the next semi-annual report.

4 . Particulate Physical and Chemical Characterization

4 . aParicle Doppler Shift Spectrometer (PDSS)

During the last 6 months, the internal calibration of the PDSS

has been improved by a factor of four so that the maximum expected

18
error in a 5 to 18 ym diameter dioctylphthalate_aerosol measurement is ± 0.05 ym.

Much of the 0.2 ym error mentioned in the last report turned out

to be due to an air flow effect which occurs when the entire

horizontal cross-section of the chamber surrounding the scattering

region is not homogeneously filled with aerosol. This filling

condition had not been met by most chamber designs used up to

this time.

Effects due to temperature gradients and chamber walls were shown

by theoretical and experimental studies to be insignificant.

The fact that air flow velocities as small as 0.004 cm/s can be

measured illustrates the capability of the PDSS to detect systematic errors affecting size measurements. Our work has uniquely

demonstrated the measurement of air flow induced by individual

small (5 to 20 ym) particles.

We believe that the size measurement capability of the PDSS can be

extended down to 0.5 ym or below by taking advantage of the

increase in settling velocity in a partial vacuum due to slip.

Since January, we have designed and installed a vacuum system

for use in conjunction with the PDSS. Experiments to measure

the slip correction to the settling velocity, as well as diffusion

by Brownian motion at atmospheric to a few torr pressure, will

start soon.

4 .b . Nonspherical Particles

Numerical calculation techniques have been developed to predict

the optical scattering properties of nonspherical particles.

These programs have been developed by modification of several

techniques which have appeared in the literature in the last two

years. NBS now has the capability to calculate the optical

scattering properties of a variety of nonspherical particles,

as a function of particle shape, size and index of refraction.

19
This calculation will be used to evaluate the performance of light

scattering particle sizing instruments when they are measuring

nonspherical particles, and will be applied to several light

scattering instruments such as the forward-angle-ratio-light

scattering particle sizing instrument. In addition, we have

theoretically evaluated several optical techniques for the

detection and identification of nonsherical particles. Work will

continue in these areas during the next reporting period and a more detailed report will be provided at that time.

4.d.e. Development of Air Supported Plasmas

The air plasma torch is especially feasible for use in direct

monitoring of airborne heavy metals since air serves simultaneously

as the sample and plasma gas. If air contains any heavy metals,

these heavy metals will be excited by the plasma flame and will

emit the spectrum characteristic of the element in the air.

This emission can be recorded by using a suitable spectrometer and

recorder. The peak heights of the chart output are directly

proportional to the concentrations of the elements in the sample.

The detection limits for Hg and Pb , using a laboratory unit for

3 3 direct monitoring of airborne samples, are 30 yg/m and 20 yg/m , respectively

.

In addition, the air plasma direct monitoring system can be

produced as a small portable unit. Development of the air supported

plasma torch has reached a point where construction of a portable

instrument for direct monitoring of heavy metals, particularly

Pb in air, can be seriously considered. The torch and its associated electronics can be miniaturized to a degree which will make

a truly protable monitor for Pb concentrations (and probably also

for Hg concentrations) in ambient air.

20
5. Particulates on Glass Fiber Filters

Pb in Filter Strips for. Monitoring Ambient Air Quality

The need for monitoring the lead particulate content of ambient

air has been accompanied by the need for accurate standards and

methods of analysis. A proposed SRM for lead on micro-quartz

glass fiber strips at three dose levels were prepared in nominal

concentrations of 100, 300, and 1500 yg per strip, and analyzed by

linear sweep voltammetry. A tentative reference method has been

proposed by EPA for analysis of these materials by atomic absorption (AAS) . However, the proposed AAS method may be subiect to

a bias of undetermined magnitude by undissolved solids from the

glass filter matrix. Voltammetry, being free of this type interference, was selected as an alternate method of analysis to

provide data in support of certification. Although a reference

procedure completely different from the method proposed for AAS

would have been more suitable, an effort was made to follow the

AAS procedure as closely as possible.

Concentration results for the proposed materials are summarized in

Table 2. Residual lead in four of the analyzed filters was

determined after extraction from the filters (by re-leaching

and sonifying with dilute • nitric acid). The amount of residual

lead found was less than 1 yg/strip for all of the filters re-analyzed,

indicating excellent recoveries.

Before final certification of the proposed materials can be completed, the effect of undissolved solids from the glass filter

matrix on AAS analysis must be determined.

The necessary measurements to make this assessment will be made

during the next reporting period.

21
Table 2

Lead in Glass Fiber Strips

Std. A. Std . B

302.9

28

Std . C

Mean (yg/strip) 1505.2

n

99.7

26 28

12.7

0 . 8 %

Std. Dev. (yg/strip)

Re I- Std. Dev.

1.6

1 . 6 %

5.4

1 . 8 %

6 . Urban Air Particulate, Washington, DC Sample

NBS SRM 1648, Urban Air Particulate Matter, collected in the

St. Louis area, has been certified for a number of elements and

has been available since March of 1979. A copy of the certificate

for this SRM was published in the last semi-annual report.

The collection of the Washington, DC Urban Particulate Sample

was initiated approximately two years ago. During the summer of

1978 several bags were removed from the collection facility to

estimate the amount of material collected and to perform preliminary

inorganic and organic analyses. During the summer of 1979, a similar study was conducted. Based on these two evaluations, it

now appears that by September or October of 1979, approximately

40 pounds of urban particulate materials will have been collected

in the Washington sampling program. It is felt that this is a sufficient amount of material and thus the facility will be shut

down, the bags removed, and the particulate matter collected from

the bags during the fall of 1979.

Preliminary inorganic and organic analyses of the material in the

Washington sample indicates that the inorganic composition is

different but not in any major way from that collected in St. Louis.

The organic composition of the Washington material appears to be

about a factor of 2 greater than that in the St. Louis collection,

but this difference may be due to the age of the sample and the

method of sample preparation prior to analysis, which was far

more extensive for the St. Louis collection than was done for

22
this trial sample for the Washington collection. Based on the

preliminary analysis, it appears that the Washington sample can

be used in two ways. It can be retained as a second sample to

be made available after the sale of the St. Louis material.

Alternatively, the Washington sample could be issued as an organicurban-air-particulate characterized only for its organic composition and provided in sufficient quantity to be used as a standard

for organic analysis. Ultimate determination of the use of the

material and the nature of its characterization will have to be

made after the sample is removed from the bags, and a more detailed

preliminary analysis has been completed. This determination

should be made in time for the next semi-annual report.

7 . Develop SRMs for Coal Conversion Processes and Materials

Balance Determinations

Three sulfur species in coal have been reported, pyritic sulfur

(FeS

2

) , sulfate sulfur (FeSO^) and organic sulfur. In these

experiments, sulfur and iron emission intensity versus temperature

curve were monitored. The method used in this work is based on

the detection of differences in vaporization of various chemical

species at atmospheric pressure, using plasma emission spectrometry

to detect the vaporized element. From the experiments four sulfur

species, FeS

2

, FeSO^, organic sulfur and low evaporation temperature sulfur were observed. The low temperature species starts

to evaporate at approximately 28 °C. Western Coal (SRM 1635) has

been found to contain about 18 times more of the low temperature

species than Pennsylvania Coal (SRM 1632a) . In the future measurements will be made using two monochromators simultaneously to

detect the sulfur and iron or other combination of elements.

23
A preliminary analysis has been performed on techniques which

might be used in analyzing organic surface layers on coalconversion particulates. The two techniques investigated were

the micro-Raman technique, and a proposed technique of differential

backscattering from single particles. The effectiveness of the

micro-Raman technique in analyzing surface layers on single particles

is still under investigation and preliminary results of this

investigation were presented in the last semi-annual report and

are contained in BCKa and b of this report.

The differential backscattering technique has been studied by

optical scattering, theoretical calculations to predict the

effectiveness of detecting and identifying organic layers on

single particulates. Preliminary analysis of this technique indicates that it would be worthy of further experimental evaluation

and an investigation of this type is planned for the next semiannual period. The instrumentation to be used in this analysis

is similar to the micro-Raman optical system, but used in a configuration such that the total backscattered intensity from a particle is collected as a function of the incident wavelength.

An absorption spectra of the particle, detected by backscattered

intensities,, is obtained. The major optical noise component in this

technique is the specular backscattering from the substrate and

the possibility of measuring a signal in the presence of this

background can only be evaluated by experimental techniques,

which will be reported in the next semi-annual report.

8 . Development of an Oil Shale SRM

Samples of an homogenized oil shale material were supplied

by T. Gills of the Inorganic Analytical Research Division. One

of these samples was Co^ - irradiated , the other was not. Twenty

grams of each material were separately extracted with 50 mL of

methylene chloride and the extracts evaporated to 100 yL. Both

concentrates were analyzed by gas chromatography using high

resolution glass capillary columns and visually identical chromatograms

24
were obtained. Thus the potential exists for a combined organic/

inorganic SRM once organic certification methods are available.

Development of an Oil Shale SRM

A quantity of Oil Shale SRM has been sterilized and set aside for

comparison with unsterilized oil shale to determined if there are

any changes in the concentration of volatile substances, both

organic and inorganic. There has been no further activity in this

project to determined the loss of volatile inorganic constituents

during the past six months.

2 S
80 -BCL -b- ENERGY RELATED AIR POLLUTANT ANALYSIS INSTRUMENTATION

1 . Development of an Instrument to Measure Airborne Sulfate

Particulate Matter

The objective of the Particulate Sulfate Instrumentation project

was to develop and evaluate a measurement system having ambient

particulate sulfur level detection sensitivity (-0.5 yg S/ m ) and

real time response suitable for mobile laboratory and aircraft

monitoring applications. The system configuration chosen for

development consists of a Flame Photometric Detector (FPD) for

measuring total sulfur preceeded by a pulsed electrostatic precipitator which modulates the particulate concentration of the sample

a selected frequency. The FPD output signal is then analyzed for

the signal component at this frequency which gives the response

of the system for particulate sulfur. This system has been

described in earlier reports in which several interferences related

to SC>2 concentration and relative humidity of the sample were noted.

These interferences have been the subject of the most recent work

on the system.

A final report on the project will be made after the system has

been evaluated in an inter-comparison study with other sulfur and

sulfate measurement systems at Washington University, St. Louis,

Missouri, in August, 1979. This report will be completed in

September 1979.

Activities in the past six months concerned a systematic study of

the effect of SC^ concentration and relative humidity on the

system response. The FPD is sensitive to the relative humidity

of the sample at the extremes (<10% r.h. and >80% r.h.). The SC^

interference is quite low, representing less than a few percent

equivalent particle sulfate response, and is a difficulty only at

very high SC^ values; however, high values may occur in undiluted

or fresh plumes. At very low SO

2 levels the FPD shows nonlinear

response and much higher noise. We are now evaluating the

26
feasibility of adding a constant level of gas phase sulfur to

bring the total FPD signal up to a better operating range for

this detector. The final report will contain a detailed

description of this modification and its effect on the system's

response

27
8 O-BCL-c -ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 . Radiocarbon as an Environmental Tracer

Work on the Portland, Oregon aerosol vegetation impact study (in

collaboration with Professor J. A- Cooper, Oregon Graduate Center

(OGC)) has been completed during the reporting period, as well as

a review of the application of carbon isotopes to carbonaceous

pollutant source discrimination for the Division of Environmental

Chemistry, ACS. A summary was presented in a special symposium

(in cooperation with OGC group) at Research Triangle Park on June

20, 1979.

The vegetative burning study represented a major step in the

successful application of the mini -radiocarbon ( 11c ) method, for

it was the first time size-fractionated particles had been measured

14 using C, and it was the first time the technique had been used

with known source impacts (field, slash, residential -wood burning)

.

The research served a) to demonstrate the validity of the method

in the field, and b) to underline the potentially serious impact

of residential wood burning on fine carbonaceous particles in

urban locales. Two important future approaches to increase the

power of the method were noted in the above studies: the use of

chemical (chemical mass balance) and isotopic (^C, ^C) selectivity, and the complementary use of accelerator mass spectrometry ( ams )

.

Although 11c and ams are presently comparable with respect to

sample size and overall precision, we believe that ams has

considerable potential for improvement, provided that sufficient

attention is given to ion source chemistry. With this in mind

we undertook a series of experiments to couple the technique of

separation and implantation of 30 keV Co

+ ions in metal foils by

Isotope Separation (IS) with high energy (-20 MeV) acceleration

14 of sputtered ions from the carbon-foil source to count C atoms

28
rather than 6-particles from their decay. Using CC^ as the sample

gas and high purity copper and aluminum as target foils, we studied

molecular ion fragmentation patterns, sputter-cleaning with a 20

keV Ar beam, and implantation-saturation phenomena. With a reasonable understanding of carbon contaminating levels and

implantation saturation O lpg/cm ) , we prepared a series of

calibration samples (oxalic acid standard and dilutions) plus one

dated archeological wood sample for radiocarbon measurement by ams

at the University of Rochester. Samples were delivered on May 15th,

14

' 1979, and we are currently awaiting C machine-time (mid-July).

Current work includes also preparations for calibration of the

new radiocarbon-dating oxalic acid standard and installation of

a dedicated data acquisition computer system. In connection

with the standard calibration, we are establishing operating

characteristics and quality control for the large (^1.6L), lowlevel "Oeschger" counter. The sample, which has already been

obtained, is derived from a 1978 sugar beet crop and its specific

activity is therefore about 30% above the previous standard

(due to nuclear testing) . We shall count several grams of carbon

with the intent of obtaining ^0.5% accuracy. The Cromenco z-2

computer system has been installed and debugged; and acquisition

of test data reflecting actual coincident and anticoincident events

has been accomplished. Programs ARDAQ and ARPULS , for acquisition

of two dimensional spectra. Energy vs ADP , net counting rates, and

test pulses, are currently being checked. Further expansion of our

data processing system will include linking the laboratory microcomputer with the NBS 1108 Digital Data Network (NBSNET) . This

expansion will provide easy access for statistical processing of

all counting data and will allow for correlation analysis of

counting results with laboratory environmental parameters, e.g.

continuously monitored room temperature, humidity and barometric

pressure

29
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

No activity in this project during the last six months.

1 . b . Estuarine Sediment, Proposed SRM 1646

No activity in this project during the last six months.

1 . c . Anions in Water SRM

No activity in this project during the last six months.

1 . d. Trace Elements in Water SRM

Certification analyses for SRM 1643, Trace Elements in Water, are

complete. The material will be available for distribution pending,

a final compilation and analysis of data.

1 . e . The Role of Internal Standardization in Analysis of Aqueous

Samples Using the Inductively Coupled Plasma (ICP) Technique

Inductively Coupled Plasma (ICP) Emission Spectrometry

Previous studies with ICP have isolated sources of non-random

variability in the measurement technique (1) . Experience has shown

that proper introduction techniques of aqueous samples can

minimize these effects. These include bracketted and averaged

standard solution integrations as well as the use of a peristialtic

pump with the cross-flow nebulizer.

30
In minimizing head pressure effects with the peristaltic pump, it

is necessary to match the number of rollers, rotation rate, tubing

size, and data integration period so that the inherent pulsation

of the pump is effectively averaged during one integration period.

For example, the following specifications have given satisfactory

results

:

Number of rollers

Rotation rate

Tubing I.D.

Resulting flow rate

Integration period

10

2 2 RPM

0.76 mm

^1 mL/min.

30 5

In cases where significant background shifts from samples to

standards occur, it is necessary to measure background intensities

on either side of the analysis line (2)

.

Present instrumentation

does not allow such a measurement without excessively lengthening

the total analysis time. Therefore, the first application of the

ICP to accurate certification determinations was limited to a few minor constituents in Coal and Coal Fly Ash, Standards Reference Materials (SRM) 1632a and 1633a, respectively. The certificates for these materials have yet to be issued in final form.

ICP results are as follows:

SRM Element x ± 2s

1632a Ca 2.16 ± 0.08 mg/

1633a Sr 818 ± 7 yg/g

1633a Zn 222 ± 8 yg/g

Contracts have recently been awarded for the new spectrometer

and computer system mentioned in the previous report. Installation

should be completed by September, 1979.

31
Eschelle Spectrometer

A continuum-source Eschelle Wavelength Modulation - Atomic absorption Spectrometer (CEWM-AA) is currently being evaluated for the

determination of trace metals in a wide variety of samples. The

CEWM-AA system offers unique advantages over existing commercial

atomic absorption instruments. In CEWM-AAS, superior background

correction is provided for all major types of spectral interferences encountered in atomic absorption analyses. Moreover,

CEWM-AAS provides accurate background compensation for larger

amounts of nonspecific source attenuation which may allow the

direct determination of trace metals in highly complex matrices

such as lubricating oils, coal, fly ash, and environmental water

samples without extensive sample preparation. However, the most

attractive feature is the potential capability of CEWM-AAS for

fully background-corrected, simultaneous multielement AA analyses

using either flame or electrothermal atomization devices.

The CEWM-AA technqiue using electrothermal atomization has been

shown to provide accurate and precise results when operated in the

single-element mode for a number of trace metals in environmental

water samples compare favorably with results obtained by a commercial, line-source AA instrument and other independent analytical

techniques. Lubricating oil samples diluted in methyl isobutyl

ketone (MIBK) have also been analyzed by CEWM-AAS for silver

and tin.

Proposed studies involving CEWM-AAS focus primarily on the optimization of analytical conditions for the determination of eight

trace metals (Cd, Cr, Cu, Pb , Mn, Ni, V, and Zn) in coal and

ultimately use this technique in the SRM Certification program

of these trace metals in other energy related materials. Additional

work is required to fully develop CEWM-AAS into a practical,

background-corrected, simultaneous multi-element AA technique for

the rapid analysis of coal and other energy-related materials.

32
2 . SRMs for Organic Analysis

2.a/b Production of an Aqueous PAH SRM

In previous reports we have described generator columns as an

ideal method for preparing saturated (standard) solutions of

individual polynuclear aromatic hydrocarbons (PAH) . Initial

plans were to issue individually certified anthracene, benz(a)-

anthracene and benzo (a)pyrene generator columns as a Standard

Reference Material (SRM) for PAH in Water by early 1979. We,

however, experienced some difficulties in finding a vendor willing

to produce this material, due to the potential hazards involved.

We have now received a bid from an interested vendor and are in

the process of awarding the contract.

Preparation of Aqueous Solutions Containing Several PAHs

Using Generator Columns

Although they do not generate saturated solutions, generator

columns coated with three or more compounds could be of more

practical value. The initial attempt to prepare such a column

met with only limited success. A column that was composed of

fifty milligrams each of phenanthrene , 1 -methylphenanthrene

,

anthracene, and 2 -methylanthracene coated on 20 grams of glass

beads, was prepared. The results of this experiment are reported

in Table 3 . After 6 liters of water had been pumped through this

"Generator Column" (G-l)

,

equilibrium had not been achieved.

The same four compounds were used in a second attempt to prepare

a generator column that would be capable of generating a stable

solution of these four components. The amounts of each compound

comprising the one percent coating on the glass beads was made to

be proportional to its aqueous solubility.

33
The results reported in Table 4 demonstrate the feasibility of

this approach. After initial conditioning, over six liters of

solution were generated with the maximum change being less than ID

percent over that range.

A third generator column (G-3), loaded with three compounds, was

prepared by the same technique used to prepare G-2. The column

was purged with 5000 mL of water at 25 °C after which a state of

equilibrium was reached. Although the concentrations generated

by this column were not equal to the equilibrium saturation

concentrations for the individual components, they never changed

by more than ±5% while more than 6000 mL of water was

purged through the column (see Table 5) . The concentrations of

the individual compounds in the effluent of this column over this

interval at 25 °C were:

Anthracene 62.1 ± 1.3 yg/kg

2 -Methylanthracene 13.3 ± 0.2

1 , 2 -Benzanthracene 10.8 ± 0.3

Table 3. Effluent Stability of "Generator Column" G-l

Water Purge

Volume

(mL)

Phenanthrene

Cone

.

(yg/kg)

1 -Methyl

phenanthrene

Cone

.

(yg/kg)

Anthracene

Cone

.

(yg/kg)

2 -Methyl

Anthracene

Cone

.

(yg/kg)

100 610 167 22.1 14 .

6

500 541 155 26.0 15.9

860 520 148 26.6 15.1

1330 506 150 29.1 15.7

4500 405 157 34.9 15 .

5

5350 388 162 35.4 15.8

5550 380 164 36.1 15.9

6400 377 170 35.2 17.7

x (1300-6400 411 161 34.1 16.1

mL) ± 53 ± 7.6 ± 2.9 ± 8.9

Maximum Range 29% 13% 19% 12%

between high and

low value

34
Table 4. Effluent Stability of "Generator Column" G-2

Water Purge Phenanthrene

Volume Cone.

fmL) (yg/kg)

1 -Methyl

phenanthrene

Cone

.

(yg/kg)

Anthracene

Cone

.

(yg/kg)

2 -Methyl

anthracene

Cone

.

(yg/kg)

25 913 96.3 12.1 12.2

550 897 73.6 20.1 9.6

2250 890 71.8 18.4 11.1

3700 906 69.9 16.6 10.2

5200 898 70.8 16.4 10.0

6320 888 74.4 16.0 8.94

7100 903 71.0 17.0 10.3

8100 876 78.1 16.5 9.24

x (2250-8100 894 72.7 16.8 10.0

mL) ± 11 ± 3.1 ± 0.9 ± 0.8

Maximum Range 1.8% 8.1% 5.8% 19.5%

between high and

low value

Table 5. Effluent Stability of "Generator Column" G-3

Water Purge 2 -Methyl

Volume Anthracene anthracene 1,2 Benzanthrac

(mL) (yg/Kg) (yg/Kg) (yg/Kg)

200 63.6 13.3 15.8

2000 58.9 11.9 14.0

5000 62.0 13.3 10.9

6000 64.1 12.9 11.0

7200 62.8 13.4 10.7

8100 62.2 13.4 11.0

9300 61.7 13.2 10 .

7

9990 60.6 13.1 10.4

11500 61.0 13.4 11.1

x (5000-11,500 62.1 13.3 10.8

mL) ± 1.3 ± 0.2 ± 0.3

Minimum Range 5.5% 3.0% 6 . 3%

between high and

low value

35
However, since saturated solutions are not generated by multi-PAH

generator columns, the composition of the generated solutions

would vary from column to column and would be a function of the

volume of water purged through the column. These factors make

the production of SRM’s via this process unlikely at this time.

2 . c . Interlaboratory Comparison Exercise

Samples of an intertidal sediment were received from W. D. MacLeod

of the NOAA National Analytical Facility in Seattle, Washington.

These samples are part of an interlaboratory comparison exercise.

The sediments were received frozen on dry ice and stored at -10 °C

until analyzed. The following parameters were to be determined:

1. Chromatographic elution patterns and data

2. Qualitative analysis

3. Quantitative analysis of single species and total

hydrocarbon content

4. Percent water in samples

5. Recovery efficiency data

The samples are being analyzed presently, using techniques

discussed in previous reports. We are participating in this

exercise to both validate our general methodology and to check

the effect of refinements to this methodology upon analyses of

potential future SRM material.

2 . d. Spectroscopic Certification Technique for Analysis of Trace

Organics in Water SRM

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 trace regulated

organics in water. This new method involves laser Raman scattering

from pollutants isolated in cryogenic matrices.

36
The work to date has been focussed on the optimization of matrix

preparation and spectroscopic techniques; proving the scientific

feasibility of this technique for the analysis of complex mixture

of volatile organics (of the type currently regulated by the EPA)

at the sub-nanogram level. Although in the developmental stages,

this technique should provide a molecular specificity and sensitivity comparable to, or better than, existing techniques currently

utilized for water quality assessment. We are investigating the

martix isolated laser Raman diagnostic for several reasons: 1)

Raman spectroscopy is vibrational spectroscopy and as such provides

a characteristic and reproducible "fingerprint" that carries

structural information to allow for the unambiguous identification

of unknown contaminants; 2) all molecules have characteristic

Raman spectra in an experimentally convenient spectral range; 3)

the matrix substrate (in this case argon) is free of organic contaminants and has no spectral interferences; it is transparent and

allows the vibrational frequencies of the trapped pollutant to

be readily compared to the gas phase values of known, pure compounds; 4) at the low temperature used, all rotational motion

is frozen out; the spectral linewidths are very sharp, so sharp

that the overlapping of bands observed in solution and in the gas

phase is not a overlapping of bands observed in solution and in

the gas phase is not a problem. The apparatus will be suitable

for interfacing directly to a gas chromatograph column for

automated sample processing.

Spectra have been routinely obtained from laboratory samples of

regulated volatile organics exhibiting spectral features of less

than 1 cm ^ width. Under these conditions molecular isomers are

readily distinguished. With our present, and far from optimum,

optics and low-power laser we can readily detect nanogram

quantities of a wide variety of volatile species.

Work is just beginning on the analysis of real work samples and

on extending this technique to the examination of PAH species.

37
References

[1] R. L. Watters, Jr. and J. A. Norris, Chapter in Applications

of Inductively Coupled Plasmas to Emission Spectroscopy , Proceedings of 1977 eastern Analytical Symposium, Franklin

Institute Press, Philadelphia, 1978.

[2] Semi-Annual Report to Environmental Protection Agency, Office

of Energy, Minerals, and Industry, EPA- IAG-D§ -E684 , p. 60,

September, 1978.

38
80 -BCM-b -ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS AND TECHNIQUES DEVELOPMENT

1 Develop Organic Standard Reference Materials for the

Calibration of Energy-Related Water Pollutant Measurement

Methods

Current measurement methodology is not adequate for the development

of SRM’s required to support effective montoring programs for

energy-related organic water pollutants. Thus, the activity in

this element is closely related to activity in the BCK-b element

and efforts over the past six months have focussed on the

development optimization of measurement methods capable of

measuring trace organics in complex matrices created by new

energy technologies so that SRM’s can be produced to support

the establishment of effective monitoring systems.

Analysis of aqueous effluents from coal conversion processes has

been initiated with the receipt of our first effluent samples.

Two aqueous effluents from Solvent Refined Coal [SRC) Pilot Plant

were analyzed for their phenol and o_-cresol concentrations. The

samples consisted of a BioUnit effluent and a Plant effluent.

As seen in Figure 4, the BioUnit effluent is treated by filtering

through sand and charcoal, and then mixing with solidification

belt cooling water to generate the Plant effluent.

39
BioUnit

effluent

1

sand filter

I

Solidification belt charcoal filter

cooling water

plant effluent

Figure 4

A simple, one -step extraction procedure was used to isolate an

acidic fraction from the samples. A 50 mL aliquot of the sample

was adjusted to pH 1 with dropwise addition of concentrated

H ? S0

4

and then extracted with 25 mL The organic extract

was dried by filtering through a cone of Na

2 SO^, and the volume

was reduced to 100 pL by evaporation under a stream of dry ^

Extraction recoveries for phenol, £-cresol, and p_-cresol were

determined in an independent experiment. The phenols were added

to H ? 0 at the 1 ppm level and extracted with CH^C^ as described

above. Absolute recoveries were determined based on chromatographic peak heights using an external standard method ( see Table

below

Table 6

Absolute recovery Recovery relative to £-cresol

Sample phenol o-cresol p_-cresol phenol o-cresol

14M-1A 53 % 11 % 70 % 0.75 1.01

14M-1B 51 69 68 0.75 1.01

14M-1C 57 75 72 0.79 1.04

54±3 72± 3 7 0± 2 0. 76±0. 02 1 . 0 2±0 . 0

40
An internal standard method was used for quantitative determinations. Preliminary single ion monitoring (SIM) gas chromatographic/

mass spectrometric analysis of the BioUnit and Plant effluent

extracts revealed the presence of phenol and oycresol, and a barely

detectable amount of £-cresol (see Figure 5) . Since the p_-cresol

was present at a level at least 2 orders of magnitude lower than

the phenol and oycresol, it was chosen as the internal standard.

Figure 5. SIM analysis of SRC BioUnit effluent acids.

41
£-Cresol was added to aliquots of the BioUnit and Plant effluents

at the 1 ppm level. The samples were extracted (in duplicate)

and analyzed by gas chromatography/mass spectrometry with selected

ion monitoring. Gas chromatographic separations were carried out

on a 30m x 0.3 mm id SP-1000 wall coated open tubular capillary

column operated isothermally at 190 °C. Although the o-cresol

and phenol are not completely resolved under these conditions,

the use of selected ion monitoring allows determination of each

compound free of interferences from the other. The molecular

ions for phenol (m/e 94) and o_ and £-cresol (m/e 108) were

monitored over the course of the chromatographic run. Peak areas

for the phenol, oycresol, and £-cresol were determined after each

run. Phenol and o-cresol concentrations were determined from the

corresponding peak areas, the internal standard concentration,

the relative extraction recoveries, and relative response factors

for the phenol and o_-cresol relative to p_-cresol which were

determined independently. The results are summarized in

Table 7.

42
Table 7

SRC Plant Effluent H^O

Sample Phenol Cone(ppb) o_-Cresol Cone

PE-15M-A 19.6 1.98

PE-15M-A 18.8 1.98

PE-15M-B 18.4 2.15

PE-15M-B 18.3 2.38

X= 18.3 ± 0.59 2.12 ±

SRC BioUnit Effluent H^O

Sample Phenol Cone. Cppb) o-Cresol Cone.

BU-16M-A 37.9 2.94

BU-16M-A 40.9 3.52

BU-16M-B 371.1 3.35

BU-16M-B 36.7 3.23

X- 58.2 ± 1.9 3.26 ±

(ppb)

0.19

Cppb)

0.24

43
80 -BCN- ENERGY RELATED POLLUTANTS AND EFFECTS MONITORING AND

ASSOCIATED METHODS' AND TECHNIQUES DEVELOPMENT

1 . Radiological Pollutant Quality Assurance

The goal of the program is to provide measurement traceability,

through the U. S. Environmental Protection Agency at Las Vegas

(EPA-LV) , for certain radionuclides not included in other programs.

These radionuclides were chosen because they are released into the

environment from nuclear power reactors (such as light-water

reactors), coal burning plants, or other, related, sources. The

program for FY 76-80 is summarized in Table 8.

44
Table 8

Radiological Pollutant Quality Assurance 3- Performing Agency: National Bureau of Standards

(Revised Milestones as of June 1979)

A - due ; k

Task 1. Radiological

calibrated radioactive

materials FY 76

1.1 Establish lab i

facility

1.2 210

Po solution k

1.3 226 Ra soil,

Mixed gamma solution,

239y Pu solution

1.4 Mixed gamma soil

1.5 Natural U solution,.

241 Pu soution

1.6 Fly ash from coal 0

1.7 2 ^ 2 Th solution,

Mixed radionuclide solutions

1.8 2 "^Pb solution

completed

FY 77 FY 78 FY 79 FY 80

k

k

k

k

k

k

k

k

A

A

£ Issuances of all Standards are subject to satisfactory performance

as defined by NBS Standard Reference Material criteria.

bAn additional $31k was allocated for (1) traceability testing,

which will be a continuing program, and (2) preparation of the

fly ash standard.

4 5
l.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 ingrowth of americium-241 .

1 . b . Fly Ash from Coal Combustion

Fly ash from the combustion of eastern United States coal has been

assayed for radium-226 and radium-228. The material has been

checked for homogeneity, packaged, and sent to EPA-LV. Radium-226

was assayed both by radon counting of radiochemically processed

samples and nondestructively by Ge (Li) - detector y-ray spectrometry.

The radium-228 concentration was determined by Ge (Li) -detector y-ray

rpectrometry of the actinium- 228 , bismuth-212, lead-212, and thallium-208 progeny of radium-228.

A second set of y-ray spectrometric measurements have been made to

determine whether the radioactive equilibrium between thorium-232

and radium-228 was disturbed during combustion of the coal. The

radium-228 concentration was found not to have changed during the

eight-month period between the two sets of y-ray emission-rate

measurements. The report of calibration for this material is being

prepared

.

1 . c . Thorium-232 Solution

Approximately 220 ampoules containing a solution of aged thorium-232

nitrate have been prepared. Six of these ampoules have been assayed

by mass spectrometry, and a report of calibration is being prepared

to accompany 200 ampoules of solution to EPA-LV.

1 . d . Mixed Radionuclide Solutions

The assayed components of a forthcoming mixed radionuclide solution,

containing tritium, strontium- 90 , cesium-134, radium-226, radium-228,

46
and natural uranium, are being assembled. Two solutions with different radioactivity concentrations are to be prepared, and 200

ampoules of each solution are to be provided to EPA-LV.

2 Measurement Traceability Studies with the Quality Assurance

Branch of EPA-LV

The NBS conducts tests with the Quality Assurance Branch (QAB) to

ascertain whether radioactivity measurements made by the QAB are

traceable to NBS. These studies are on radioactive test sources,

with knownbut undisclosed values, that are sent to the QAB by NBS,

and on radioactivity standards prepared by the QAB and sent to NBS

for confirmatory measurements. The criteria for conducting the

studies are given in an appendix to the NBS-EPA interagency agreement of April 1976.

During this six-month reporting period, NBS has provided the QAB

with seven test sources, and no results have been reported to NBS.

The seven test sources are described in Table 9.

it

47
TABLE 9

Test Sources Provided to the Quality Assurance Branch

(EPA-LV) by NBS During the First Six Months o£ 1979.

Parent

Radionuclides

Form Month Sent Remarks

Hydrogen3

Solution February

Manganese- 54 Solution March

Strontium- 89 Solution February Contains strontium-90

and stable calcium as

interferences

Strontium-90 Solution February Contains barium-133

and stable calcium as

interferences

Thor ium- 2 32 Solution March

Americium-241 Solution February

Plutonium- 242 Solution May

48