NBS

PUBLICATIONS

i

A 1 1 1 2 L314T1

NA1|'L INST OF STANDARDS & TECH R.I.C.

. c All 102631491

Frank E/Collectlon and analysis o QC100 -U56 NO.87-3527 1987 V19 C 1 NBS-P uoiiecfion and Analysis of

Organic Compounds in Air: An

Annotated Bibliography

[1976-1986]

Frank E. Jones

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Engineering Laboratory

Center for Chemical Engineering

Chemical Process Metrology Division

Process Sensing Group

Gaithersburg, MD 20899

February 1987

Prepared for:

QC

' Army

mical Research, Development and Engineering Center

100 rdeen Proving Ground, MD 21010-5423

«U56

87-3527

1987

c.2
ifcSS
NBSIR 87-3527

Collection and Analysis of

Organic Compounds in Air: An

Annotated Bibliography

[1976-1986]

Frank E. Jones

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Engineering Laboratory

Center for Chemical Engineering

Chemical Process Metrology Division

Process Sensing Group

Gaithersburg, MD 20899

February 1987

Prepared for: U.S. Army

Chemical Research, Development and Engineering Center

Aberdeen Proving Ground, MD 21010-5423

research

information CENTER NBSIR 87-3527 MSS/,

COLLECTION AND ANALYSIS OF

ORGANIC COMPOUNDS IN AIR: AN

ANNOTATED BIBLIOGRAPHY

[1978-1886]

Frank E. Jones

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Engineering Laboratory

Center for Chemical Engineering

Chemical Process Metrology Division

Process Sensing Group

Gaithersburg, MD 20899

February 1987

Prepared for: U.S. Army

Chemical Research, Development and Engineering Center

Aberdeen Proving Ground, MD 21010-5423

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

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

Collection and Analysis of Organic

Compounds in Air:

An Annotated Bibliography (1976-1986)

Frank E. Jones

Process Sensing Group

Chemical Process Metrology Division

National Bureau of Standards

Gaithersburg, MD 20899

CONTENTS

Page

Abstract ii

Introduction iii

A. General 1

B. Standard Operating Procedures 27

Subject Index 33

Author Index 46
ABSTRACT

This is a selected and annotated bibliography of sources of methodology

for the collection and analysis of volatile and semi-volatile organic compounds present in air. The most prevalent methodology is the collection and

preconcentration of organic compounds in a tube or cartridge containing an

adsorbent, and subsequent thermal desorption of the collected compounds on

the column of a gas chromatograph (GC), GC/mass spectrometer (MS), or

GC/MS/computer system for analysis. The performance of adsorbents such as

porous polymer adsorbents, and the optimization and standardization of

methodology are of particular interest. The bibliography comprises 68

general citations and 17 standard operating procedures.

Keywords: Adsorption; adsorbent cartridges; bibliography; analysis;

GC/MS/computer systems; porous polymer adsorbents; standardized methodology;

thermal desorption; volatile and semi -volatile organic compounds

ii
INTRODUCTION

The collection and analysis of volatile and semi-volatile organic compounds present in air is of broad interest and of particular interest in

ambient air pollution. The most prevalent methodology is the collection and

preconcentration of organic compounds in a tube or cartridge containing an

adsorbent (such as Tenax-GC), and subsequent thermal desorption of the collected compounds on to the column of a gas chromatograph (GC), GC/mass

spectrometer (MS), or GC/MS/computer system for analysis. One of the objectives of the work of which this annotated bibliography is a part is the

optimization and standardization of the methodology for the collection and

analysis of the volatile and semi-volatile organic compounds of interest.

References to relevant literature were acquired through a computer

search of various data bases by the Research Information Center of the

National Bureau of Standards; this initial collection of references was

supplemented from current literature and other sources. The period 1976-

1986 was searched in order to concentrate on recent published advances in

methodology and instrumentation.

The bibliography comprise 68 general citations and 17 standard operating procedures. It was not the intent to be exhaustive but rather to be

selective in citing items of particular or related relevance to the work of

interest. Likewise, the summaries for the citations include items of particular or related interest.

iii
In order to specify adequately procedures and techniques, identification of products and apparatus have been made. Such identification does not

imply recommendation or endorsement by the National Bureau of Standards, nor

does it imply that the products or apparatus identified are necessarily the

best available for the purpose. Also, opinions expressed or implied in the

summaries are those of the authors of the individual citations.

The author gratefully acknowledges the contributions of Diane

Cunningham in making the computer search, the encouragement of Dr. Amnon

Birenzvige, the support of the U.S. Army Chemical Research, Development and

Engineering Command, and the typing of the manuscript by Deb Musumeci, Gina

Kline, and Chris Mueller.

iv
A. GENERAL

[1] Ackley, M. W.

Residence Time Model for Respirator Sorbent Beds

Am. Ind. Hyg. Assoc. J. 46, 679-689 (1985)

In this article an experimental sorbent bed residence time model was developed for collecting reliable sorbent bed performance data. The model is

based on the unique relationship between breakthrough time and bed residence

time. The author claims that the resulting fundamental sorbent characteristics can be applied to predict the performance of any cartridge or canister

with knowledge of the concentration of the contaminant, the volume of the

adsorbent, and the airflow rate. The ASC I/SCL system was used to demonstrate the model and its application. The author concluded that the model

"(1) provides fundamental performance characteristics for any sorbent/gas or sorbent/vapor system; (2) can be used to reliably predict the performance of

respirator cartridges and canisters knowing only the contaminant concentration, flow rate and volume of adsorbent; (3) is applicable to both adsorption and chemisorption processes and can be structured to include the effects; (4) does not account for wall heat transfer effects.”

[2] Alder, J. F., Hildebrand, E. A., and Sykes, J. A. W.

Automatic Two-Stage Thermal Desorption Gas Chromatography for LowVolatility Organic Vapour Determination

Analyst 110, 769-773 (1985)

This paper reports on an investigation of the use of a commercially available automatic thermal desorption device for determining the vapor, at trace

levels, from low-volatility compounds. The desorption device was coupled

through a heated stainless steel transfer pipe to a gas chromatograph fitted

with a column containing 4-5% of free fatty acid phase on Chromosorb W AW

DMCS (60-80 mesh). The output of the flame ionization detector was fed

through the gas chromatograph electronics to a recording integrator. The

automatic two-phase thermal desorption gas chromatography mode of operation

was found to be useful in determining the vapor from methyl salicylate over

the range Ing-lyg, and 2,2’ -dichlorodi ethyl ether over the range lOng-IOOyg.

The authors stated that there was a problem due to memory effects, which

could be accommodated. They suggested that some equipment modification

would be required before the routine application of the method to relatively

involatile compounds would be possible. The authors declared that there was no intention of any direct or implied criticism of the manufacturer of the

device or of the design of the instrument.

[3]

Anderson, K., Hallgren, C., Levin, J.-0., and Nilsson, C.-A.

Determination of Ethylenediamine in Air Using Reagent-Coated Adsorbent

Tubes and High-Performance Liquid Chromatography, on the 1 -Naphthylisothiourea Derivative

Am. Ind. Hyg. Assoc. J. 46, 225-229 (1985)

A method for trace analysis of ethylenediamine in air was developed to overcome problems encountered in the analysis of amines: 1) amines are difficult

to collect and analyze since they are sensitive to oxidation and

degradation; 2) the low ultra-violet absorptivity of this functional group

limits the applicability of high-performance liquid chromatographic (HPLC)
methods to the analysis of amines. The reported chemisorption method uses

1 -naphthylisothiocyanate coated on XAD-2 to trap ethylenediamine. The 1-

naphthyl isothiourea derivative formed is subsequently desorbed using tetrahydrofuran and is directly injected into an HPLC. Derivatization of the

amine directly upon collection stabilizes the molecule, facilitating transportation and storage prior to analysis and final chromatographic separation. The minimum detectable quantity corresponding to peak height equal to

four times the noise level was approximately one nanogram for a pure standard of the derivative at 254 nanometers, and 0.3 nanogram at 229

nanometers.

[4] Bailey, A., and Hollingdale-Smith, P.A.

Passive Sampling and Dosimetry

In Trace-Organic Sample Handling , E. Reid, editor (John Wiley and Sons,

Halsted Press, Chichester, England, 1981) pp. 43-50

Work carried out at the Chemical Defense Establishment (C.D.E.), Porton

Down, Salisbury, U.K., on the development of a passive sampling device for

personal atmospheric monitoring is described. The basis of the sampling

method is the transfer of gas or vapor from the air being sampled to a sink;

the rate is defined by a diffusional resistance. The C.D.E. diffusion

sampler uses a porous polypropylene film as the transfer membrane and charcoal cloth as the adsorptive sink. Variations in sampling rate with changes

in temperature, humidity, and air velocity; storage stability; and sample

recovery are discussed. Results obtained from passive samplers and dynamic

samplers were comparable.

[5] Bisgaard, P., Molhave, L., Reitz, B., and Wilhardt, P.

A Method for Personal Sampling and Analysis of Nanogram Amounts of

Formaldehyde in Air

Am. Ind. Hyg. Assoc. J. 45, 425-429 (1984)

This article describes a method, and tests thereof, for monitoring exposure

to formaldehyde at nanogram levels. The method forms the basis of a commercial sampling tube; it involves collection on Chromosorb W coated with 0.6$

7-amino-5-hydroxy-2-naphthalenesulfonic acid in concentrated sulfuric acid,

desorption with concentrated sulfuric acid, and colorimetric or fluorimetric

determination of the reaction product. The standard sampling tube consists

of three sections: 1) the first section containing a drying agent which

removes water vapor from the air sample; 2) a second section containing the

solid sorbent material which forms a fluorescent compound during exposure to

formaldehyde; and 3) a back-up section containing the same sorbent material.

The sampling- tubes were exposed to formaldehyde concentrations in the range

0.2-0. 8 mg/m. Most tests for the evaluation of the sampling and analytical

principle were performed in dry air and without drying sections, leaving the

problem of finding a suitable desiccant to be solved later. Studies of

capacity, interference, and stability of the formaldehyde samples were made.

The authors conclude that both fluorimetric and colorimetric determinations

in acid solution were adequate for measurements of small amounts of formaldehyde in air; however, if measurements of more than 15 minutes duration are taken the adequacy of a desiccant still remains to be verified.

[6] Bishop, E. C., and Hossain, M. A.

Field Comparison Between Two Nitrous Oxide (N„0)

Passive Monitors and Conventional Sampling Methods

2
Am. Ind. Hyg. Assoc. J. 45, 812-816 (1984)

The purpose of the investigation reported in this article was to evaluate

two commercial passive diffusion monitors (referred to here as R and S) for

use in determining waste nitrous oxide (N^O) concentrations in U.S. Air

Force medical, dental, and veterinary facilities. A unique chamber for

field evaluations was designed, built, and used. The chamber exposed all

test devices to the same environment and provided for real-time monitoring

of exposure agents; a large port on the side of the chamber was connected to an infrared analyzer to continuously monitor the N^O concentration. The R

monitor utilizes the principle of molecular diffusion with a molecular sieve

as the collection medium. Two sections of adsorbent were packed in an aluminum tube covered with plastic tubing. The S monitor contained a desiccant section preceding the molecular sieve sorbent section. Both monitors

were thermally desorbed and the samples were analyzed by IR by the respective manufacturers. Bag samples collected by withdrawing air from the

chamber were analyzed by the USAF. The results, covering the range 4 to 330

ppm N^O, indicated an "overall accuracy" of +30.5$, +_40$, and +^1 80% for the

R monitor, the bag sampler, and the S sensor, respectively.

[7] Bishop, R. W., Ayers, T. A., and Rinehart, D. S.

The Use of a Solid Adsorbent as a Collection Medium for TNT and RDX

Vapors

Am. Ind. Hyg. Assoc. J. 42, 586-589 (1981)

The study reported in this article was conducted to determine the feasibility of using a tube containing a solid adsorbent for the efficient collection of TNT vapors and RDX vapors. Sampled air was pumped through sorbent

tubes containing Tenax-GC resin 20/35 mesh; this sorbent was selected based

on its sorption capability, inertness, and hydrophobicity

. ^Florisil was also investigated as a sorbent. Gas chromatography with a °^Ni electron

capture detector utilizing a glass column packed with 6 % 0V-101 on 80/100

mesh Gas Chrom was used for analysis. To determine desorption efficiencies,

the front sections of several sets of sorbent tubes were spiked directly

with stock TNT/RDX acetone solutions. Acetonitrile was used for desorption.

The work demonstrated that Tenax is an effective sampling medium for collecting vapor concentrations of TNT and RDX. The vapor generation method,

involving the use of a heated generation chamber (at 200 °C) to produce

vapor concentrations of the explosives, proved to be a simple but effective

technique. The authors concluded that Florisil did not show suitable potential as a means for collecting TNT vapors or RDX vapors.

[8] Borders, R. A., Gluck, S. J., Sowle,, W. F., and Melcher, R. G.

Development and Validation of Personal Monitoring Methods for Low

Levels of Acrylonitrile in Workplace Atmosphere: II. Thermal Desorption

and Field Validation

Am. Ind. Hyg. Assoc, J. 47, 158-163 (1986)

Field validation studies for determination of acrylonitrile (AN) in air were conducted at three sites with the use of the methods developed in a com- panion article (outlined in [9]) and an intermediate thermal desorption

technique. This technique used a commercially available thermal desorber

which desorbed collected organics into a heated storage chamber; aliquots

were then injected through a gas sampling valve into a gas chromatograph.

The thermal desorption sample tubes used in these studies were designed

3
especially for the collection of acrylonitrile in the presence of less

volatile compounds. The dual-bed tube (Tenax-GC with Carbosieve B) was designed from breakthrough volume data for AN on various solid sorbents; the

purpose of the Tenax was to act as a filter for the Carbosieve B. AN was retained only slightly by Tenax and was trapped by the Carbosieve B. The

field validation studies showed that the methods developed in the laboratory

were effective in the field under a variety of conditions at concentrations

of acrylonitrile ranging from 0.05 to 5 ppm. The dual-bed collection tube

exhibited high collection efficiency and no breakthrough was observed under

any of the test conditions. High humidity and the presence of other organic

compounds did not affect the collection or recovery of AN. There was no loss in recovery for samples stored for periods of up to 56 days at room temperature. The total injection thermal desorption technique, the most

sensitive of the methods in this study, gave excellent recovery and

precision.

[9] Borders, R. A., Melcher, R. G., and Gluck, S. J.

Improved Methodology for Field Validation of Industrial Hygiene

Monitoring Methods

Am. Ind. Hyg. Assoc. J. 45_, 299-305 (1984)

This article describes a statistical method to evaluate a field validation

(of industrial hygiene monitoring methods) experiment, methodology to perform the experiment, and equipment which facilitates the experiment. For

field validation, it is necessary to prepare accurately spiked sampling

tubes which can be sampled side-by-side with a normal sample, to determine

the recovery and whether the recovery has been affected. Field spiking is

also a test of the integrity of the sampling, transportation, and analytical

procedures. The Dynamic Atmosphere Generation System (DAGS) simultaneously

produced multiple sampling tubes spiked at known concentrations without the use of a solvent (other than clean air). Two sampling manifolds are described which allow multiple field samples to be taken using one pump. The

use of the DAGS for spiking samples was found to be quite convenient and

rapid for gases and relatively volatile liquids. Both of the field spiking

manifolds were used extensively in an industrial hygiene survey for

acrylonitrile and no problems were encountered with either manifold.

[10] Brown, R. H., Harvey, R. P., Purnell, C. J., and Saunders, K. J.

A Diffusive Sampler Evaluation Protocol

Am. Ind. Hyg. Assoc. J. 45, 67-75 (1984)

The authors develop a diffusive sampler protocol the main features of which

are: 1) emphasis on determination of the accuracy of the standard atmosphere used to calibrate the samplers; 2) emphasis on field testing the

samplers in a variety of occupational environments; 3) omission of acceptance criteria based solely on accuracy. A diffusive sampler is defined as

"a device which is capable of taking samples of gas or vapor pollutants from

the atmosphere at a rate controlled by a physical process such as diffusion

through a static air layer or permeation through a membrane, but which does

not involve the active movement of the air through the sampler." The ar- ticle makes recommendations for laboratory and field tests, for estimating

sampler precision under different conditions, and for determining its

calibration factor or curve (the standard uptake rate). The various topics

treated are: uptake rate units; factors affecting uptake rate; laboratory

experiments, test apparatus; independent sampling method; determina- tion of

4
the effect of external air movement on sampler performance; determination of

the effect of exposure concentration and time on sampler performance; ex- posure to zero concentration; effect of storage; determination of the

effects of temperature, pressure, and humidity on sampler performance;

determination of the effect of potential interferents on sampler

performance; determination of standard uptake rate; field experiments including paired comparisons - personal sampling, and multiple comparisons - static sampling. Two practical examples are considered in appendices.

[11] Brown, R. H., Charlton, J., and Saunders, K. J.

The Development of an Improved Diffusive Sampler

Am. Ind. Hyg. Assoc. J. 42, 865-869 (1981)

This article describes a diffusive tube-form sampler, specifically designed

for thermal desorption without removing the adsorbent. The standard version

of the tube-form sampler consisted of a 6-mm OD, 5-mm ID stainless steel

tube 90 mm in length, containing 400 mg of Porapak Q. The air gap of 15 mm length and 5 mm ID ensured that external flow effects were minimized and

that the uptake was sufficient for convenient analysis, an extended length

of adsorbent providing capacity. Other porous polymer adsorbents such as Tenax-GC were used successfully in trials not reported in this article. The

samplers were calibrated by exposure to benzene, removal from the exposure

chamber usually after 8 hours, and two-stage thermal desorption onto a gas

chromatograph column. The total amount desorbed was determined

gravimetrically . Laboratory trials were supplemented by field trials in

parallel with a conventional pumped adsorption tube sampling system. The

diffusive samplers eliminated the need for a pump and they could be used for

both static and personal monitoring. Relative humidity did not affect the

uptake, temperature had a small but insignificant effect for the range of

temperatures at which monitoring is likely to be carried out. The authors

have successfully used diffusive samplers with other analytes including

styrene and acrylonitrile in addition to benzene.

[12] Brown, R. H., and Walkin, K. T.

Performance of a Tube-Type Diffusive Sampler for Organic Vapours in

Air

Anal. Proc. Fifth International SAC Conference, May, 1981, pp. 205-

208 .

This article describes the contribution of the Health and Safety Executive,

Occupational Medicine and Hygiene Laboratories, London, Great Britain, to

the development of the tube- type diffusive sampler described in [11]. The

sampler has a low sampling rate of about 1 nanogram (ng)/ppm/min, equivalent

to an air volume of about 1 mL/min. For benzene sampled in a Tenax tube

with a 2.3-cm air gap, the uptake rate was 1.4 +0.06 ng/ppm/min over the

range 1.3-78.6 ppm (2 hour exposure); for 50 ppm of benzene sampled on

Tenax, as above, the uptake rate was 1.4 +G.04 ng/ppm/min over the range 13-

95/S relative humidity at 20 °C. The authors observed a decrease in uptake

with time of exposure which they attributed for (Tenax, Porapak, and XAD-2)

to a small vapor pressure at the adsorbent surface which would reduce the

concentration gradient of pollutant and hence the rate of adsorption would

be reduced; they did not consider the observed change to be very serious.

The moderate effect observed with benzene sampled on Tenax might be reduced

by substituting a stronger adsorbent such as Porapak N. The prinicpal advantages of the tube-type diffusive sampler over badge-type designs are a

5
much reduced face-velocity effect and the ease of automated analysis. The

principal advantages over other diffusive tube devices were increased capacity and the elimination of turbulence effects within the tube.

[13] Brown, R. H., and Purnell, C. J.

Collection and Analysis of Trace Organic Vapour Pollutants in Ambient

Atmospheres; The Performance of a Tenax-GC Adsorbent Tube

J. Chromatogr. 178, 79-90 (1979)

This article presents an analysis of the adsorption characteristics of

Tenax-GC. Most chromatographic methods for the measurement of the relatively low concentrations of organic contaminants in ambient air require a concentration step before the actual analysis. One of the most frequently

used concentration techniques is adsorption on solid adsorbents, particularly the use of a porous polymer adsorbent, and direct thermal desorption into

the gas chromatograph. The advantages of the latter technique are principally high sensitivity and the absence of a solvent peak in the analysis.

The most popular adsorbent has been Tenax-GC, a polymer of 2,6-diphenyl-pphenylene oxide, the principal advantages of which are its high temperature

stability and its extremely low affinity for water vapor. The absorbent

tube used in the studies described in this article was constructed of stainless steel tubing (75 mm x 4.5 mm ID) and contained 0.13 jK).01 gram of 40-60

mesh Tenax-GC. Before use, the tubes were conditioned under nitrogen at 250

250 °C for 16 hours. The following topics were investigated: safe sampling

volumes; direct and indirect measurement of breakthrough volume; extrapolation of retention volume data; influence of flow-rate on breakthrough volumes; influence of vapor concentration on breakthrough volumes; the effects

of temperature and humidity on breakthrough volumes; determination of safe

sampling volumes (defined as 50% of the measured retention volume). Safe

sampling volumes for 71 organic compounds and a plot for the interpolation

of estimated values for unlisted compounds are presented. Temperature

markedly affected breakthrough, breakthrough was virtually independent of

humidity.

[14] Brownlow, C. S., and Que Hee, S. S.

Comparison of Solid Sampling Media for Aroclor 1254 Vapor Under Dry

and Humid Conditions

Am. Ind. Hyg. Assoc. J. 46, 421-426 (1985)

It was the aim of the study reported in this article to compare the sampling

ability for Aroclor 1254 vapor of XAD-2, Tenax-GC, and Chromosorb 102

against deactivated Florisil under similar conditions of sampling both in

the presence and absence of humidity. The sampling tubes were prepared by

packing 100 mg. of the sorbent into clean Pyrex tubing (50 to 70 mm long; 6- mm OD; 3~mm ID). Non-silanized glass wool plugs before and following the

sampling medium held the sorbents in place. Only 50 mg of sorbent was used

in the Tenax-GC tubes because of the higher pressure drop. Each tube was vortexed for 10 seconds to ensure uniform packing. Triplicate sorbent tubes

were spiked with either 0.1 yL (2.4 yg) or 4 yL (9.6 yg) Aroclor 1254 in ~ hexane, corresponding to atmospheric concentrations of 10 yg/m and 40 yg/nr

of Aroclor 1254 when sampled at 500 mL/rrr for eight hours. Another set of

sampling tubes was saturated with water before spiking to assess the effect

of humidity. Efficiency of recovery with hexane was determined by comparing

solutions from spiked tubes with spiked 5-mL hexane solutions and also with

calibration. Methanol also was evaluated as a desorption solvent. The

6
authors concluded that Tenax-GC tended to be the poorest sorbent of the

four, Chromosorb 102 gave precise results most consistently and so it was chosen as the sampling medium to be compared with deactivated Florisil in

vapor generation studies. Chromosorb 102 (60/80 mesh) was found to be as good a sampling sorbent for Aroclor 1 25-4 vapor as deactivated Florisil

(30/60mesh), but recoveries were less precise at 90% relative humidity.

[15] Bunch, J. E., and Pellizzari, E. D. Evaluation of Chromotographic Sorbents Used in Air Pollution Studies

J. Chromatogr. 186 , 811-829 (1979)

Laboratory and field experiments, performed to permit detection of potential

in situ formation of chemical substances or their decomposition on the sur- face of Tenax-GC, XAD-2, and carbon sorbents, are described in this article.

Tenax-GC was purified by Soxhlet extraction with methanol and n-pentane,

respectively, for 18 hours; after drying under nitrogen atmosphere, the sor- bent was heated to 150 °C for 2 hours in a vacuum oven, sized into a 35-60

mesh range, and packed into glass tubes. The sample cartridges were preconditioned by heating to 275 °C for 20 minutes under a helium purge of 20-30

mL/min; after cooling in precleaned culture tubes, the containers were sealed to prevent contamination of the cartridges. XAD-2 sorbent cartridges

were prepared in the same manner as was Tenax-GC except that thermal preconditioning was accomplished at 200 °C for 2 hours. Replicate samples and

blanks were analyzed by GC equipped with flame ionization detection. Vapors

were transferred from the cartridge sampler to the analytical system by

thermal desorption. A GLC with electron-capture detection and a 0 . 2%

Carbowax 1500 on Carbopack C column was also used. A GLC-MS-computer system

was used for analyzing Tenax-GC cartridges when structural confirmation was required. Halogenated hydrocarbons, in trace quantities, were produced in

reactions between bromine, chlorine, 2-butene, and cyclohexene, but not with

ethylene or propylene. These in situ reactions were prevented by using a glass fiber filter impregnated with sodium thiosulfate in front of the sor- bent cartridge to quench the reactive gases.

[16] Cox, P. C., and Brown, R. H.

A Personal Sampling Method for the Determination of Nitrous Oxide

Exposure

Am. Ind. Hyg. Assoc. J. 45, 345-350 (1984)

The suitability of a diffusive sampler, described in [11], for the determination of time weighted personal and static exposures to nitrous oxide was

investigated. The sampler consisted of a 6-mm 0D, 5-mm ID stainless steel

tube 90 mm in length, containing 950 mg of molecular sieve 5A. This

molecular sieve was chosen as the adsorbent based on published work on nitrous oxide; the uniform cavities selectively adsorb molecules of diameter

less than 5 angstroms and retain them until displaced by heat, for example.

Calibration of the sampler for various concentrations of nitrous oxide and

various periods of exposure was necessitated by the dose-dependent nature of

the sampler. The effects of humidity changes on diffusive uptake were found

to be negligible. The mean precision (coefficient of variation) for samples

taken diffusively was 9 %, that of spiked samples was 3.7?; this precision

was similar to that for conventional pump and test tube methods. The diffusive method was preferred because of its simplicity and convenience of

use.

7
[17] Coyne, L. B., Cook, R. E., Nann, J. R., Bouyoucos, S., McDonald,

0. F., and Baldwin, C. L.

Formaldehyde: A Comparative Evaluation of Four Monitoring Methods

Am. Ind. Hyg. Assoc. J. 46, 609-619 (1985)

Laboratory and field tests of the performances of four different formaldehyde monitoring devices are described in this article. The devices evaluated were a formaldehyde badge, an impregnated charcoal tube, an impinger/

polarographic system and a formal demeter. The badge incorporated a patented

multicavity diffuser element and a specific absorbing sodium bisulfite solution in a self-contained package. The impregnated charcoal tube contained

150 mg of charcoal impregnated with a proprietary oxidizing agent, 100 mg in

the front section and 50 mg in the back section. Two standard glass midget

impingers each contained 15 mL of extra purified distilled deionized water;

the samples collected in the impingers were analyzed by polarographic reduction of the hydrazine derivative. The formaldemeter used an electrochemical

fuel cell containing two platinum electrodes to detect and measure formaldehyde concentrations. The monitoring devices were exposed to known

formaldehyde concentrations. The badge had a sensitivity of 2.8 ppm-hour

and accurately and simply determined time-weighted average (TWA) exposures;

however, the authors reported that it was not sufficiently sensitive to

measure short-term exposure limit (STEL) exposures, whereas, positive

interferences resulted if 1.3-butadiene were present. The impregnated charcoal tube had a sensitivity of 0.06 ppm (based on a 25-liter air sample

volume) and measured both TWA and STEL. The impinger/polarographic method

had a sensitivity of 0.06 ppm (based on a 20-liter air sample) and ac- curately determined the STEL; however, it was found to be not very practical

for TWA personal monitoring measurements. The formaldemeter had a sen- sitivity of 0.2 ppm; however, it responded to many interferences.

[18] Demian, B., Lam, K., Schindler, A., and Pellizzari, E. D.

Synthesis and Characterization of Porous Polyimides for Air Sampling

of Volatile Organic Compounds

In Identification and Analysis of Organic Pollutants in Air , L. H. Keith, ed. (Butterworth Publishers, Boston, MA S 1984. pp. 95-124

A range of aromatic polyimide resins were synthesized and evaluated as sor- bents for vapor phase organic analysis, as an alternative to commercially

available materials. A total of 55 different polyimide resins were prepared

by reacting pyromellitic dianhydride or benzophenonetetracaboxylic acid an- hydride with selected aromatic diamines. Laboratory tests performed to

evaluate the acceptability of each resin as sorbent for trace level organic

analysis included thermogravimetric analysis, gas chromatographic analysis

of sorbent background, and retention volume measurements by temperature

programmed gas chromatography. Sorption properties of the four most promising polyimides (designated AC-7, AC-13, AS-2, and AC1-3), and Tenax-GC as a reference sorbent, were further investigated by isothermal gas chromatographic measurements at zero surface coverage. Results for the selected polyimide sorbents in tests related to the trace analysis of organics in air were found to be comparable to or better than the corresponding values for

Tenax-GC.

[19] Dietz, E. A., Jr., and Hoffman, V. J.

Methods for Sampling and Determining Chlorotrifluoroethylene (CTFE) in

Air

8
Am. Ind. Hyg. J. 45, 382-385 (1984)

In this article, two new methods for sampling and analysis of chlorotrifluroethylene monomer (CTEE, a colorless, odorless gas) at concentrations

exceeding 1 ppm (4.8 mg/nr) time-weighted average (TWA) are compared. In

the first method, a 10-L Tedlar film bag was inflated with approximately 9L

of air using a calibrated personal pump. A 2-cc aliquot was injected into a gas chromatograph equipped with a flame ionization detector. The CTFE con- centration was inferred from peak heights or areas relative to peak height

or areas observed for standards that covered the range of interest. In the

second method, air was drawn through a two-sectioned (200/400 mg) charcoal

sample tube. The front and back sections of the charcoal tube were transferred to separate 7~mL vials along with 5 mL of toluene. After a 30-minute

desorption period with periodic agitation, about 1 mL of toluene solution

was transferred to a GC autosampler vial. CTFE concentrations were inferred

from GC responses. Prior to the selection of charcoal as the adsorbent, a qualitative screening was conducted for the following adsorbent materials:

Porapak R (31); Porapak Q (34); Tenax-GC (38); Porapak P (42); Porapak N

(48); Porapak S (60); Silicagel (60); Porapak T (64); and charcoal (99.2).

The value in parentheses is the percentage reduction of CFTE in each vial

head space as compared to a control vial. The charcoal sorption procedure

was recommended. The charcoal tube method was applied to field testing,

following the successful laboratory validation.

[20] Dillon, H. K., Fowler, W. F., Bryant, M. L., Martin, J. J., and

Sarver, E. W.

Sampling Technology

Chemical Research and Development Center, Aberdeen Proving Ground, MD,

Report No. CRDC-CR-84051 , May, 1984.

The potential utility of the (then) currently available vapors and as- sociated materials for the collection of organic vapors was evaluated in

this report. The types of samplers with specified solid sorbents that were investigated are: Minimonitor (Span, Inc.) with Tenax-GC and Porapak Q;

stainless steel sampling tube (Perkin-Elmer, Inc.) with Tenax-GC and Porapak

Q; organic vapor gas monitoring badge (SKC, Inc.) with Anasorb AK; i.e.,

Amberlite XAD-2; and the Porton Down diffusive sampler (Chemical Defence

Establishment of Great Britain) with Porapak Q on a "sticky" tape disc. The

samplers were evaluated with chemicals including: 2-chloroethyl ethyl sulfide, diisopropyl methylphosphonate (DIMP), methyl benzilate, and bis

(butoxyethyl) phosphate.

[21] Dillon, H. K., Barrett, W. J., and Eller, P. R. Solid Sorbent Sampler for White Phosphorus in Air

Am. Ind. Hyg. Assoc. J. 39_, 608-61 4 (1978)

This article describes the use of a solid sorbent sampling tube packed with

Tenax-GC (35/60 mesh) to collect samples of white (yellow) phosphorous

vapor, P^(g), from air. The sorbent material was divided into a 100-mg

sorbing section and a 50-mg backup section. Air was drawn through the sam- pling tube by a personal sampling pump. Each sorbent section was then

extracted separately into xylene. A 5~pL aliquot, removed from each extract

or diluted extract with a syringe, was introduced into a GC column packed

with 3 % OV-1 on 100/200 mesh Gas Chrom Q. The gas chromatograph was equipped with a flame photometric detector. Tenax-GC was found to be the

9
more efficient collector. An error of less than 1 0% was determined in the

measurement of phosphorus concentrations ranging from 0.05 to Q . 37 mg/m , with a lower limit for acceptable precision at about 0.01 mg/m.

Interferences from red phosphorus, phosphine, water vapor, or other common gases were not significant. Effects of variations in temperature, humidity,

pressure, sample storage and shipping conditions, and chromatographic

parameters were determined. The authors concluded that the collection of

trace amounts of P^(g) on a porous polymer such as Tenax-GC appeared to

provide a suitable substitute for the xylene impinger method.

[22] Easley, L. D., and Suggs, H. J.

The Effect of Low Flowrates on the Collection Efficiency of Hexane on Charcoal

Am. Ind. Hyg. Assoc. J. 46, 150-153 (1985)

In the investigation reported in this article, the effect on charcoal tube

collection efficiency for hexane at flowrates in the laminar, transition,

and turbulent flow modes was studied. A sample mixture of n-hexane in

nitrogen at a concentration of 689 ppm was passed through charcoal sorbent

tubes at flowrates of 290, 580, 1710, 2860, 5400, and 6670 mL/min until the

tubes were saturated and breakthrough occurred. Two measures of collection

efficiency were used: (1) breakthrough volume, breakthrough time multiplied

by the volumetric flowrate; and (2) kinetic saturation capacity (We), grams

of vapor adsorbed per gram of adsorbent at breakthrough. Breakthrough time

was defined as the time needed for 10# of the inlet concentration to be

detected in the discharge stream. The sample tubes contained a bed of 20/40

mesh activated coconut shell charcoal, at bed weights of 200, 250, 300, and

400 mg. Each tube was vibrated with a chromatograph column vibrator for 30

seconds and then a fiberglass plug was inserted. The contaminant (hexane) was detected by a gas chromatograph equipped with a fame ionization detector. The authors concluded that, under the test conditions, there were significant differences in breakthrough volumes or kinetic saturation capacities related to flowrates (laminar, transition, or turbulent); and that a different contaminant or under different test conditions, such as lower con- centrations, could lead to different results.

[23] Elskamp, C. J., and Schultz, G. R.

A Solid Sorbent Air Sampling Procedure for Methyl-, Dimethyl-, Ethyl-,

and Diethylamine

Am. Ind. Hyg. Assoc. J. 47, 41-49 (1986).

This paper describes the development and evaluation of a solid adsorbent

tube sampler, sampling procedures, and analytical procedures for methyl-,

dimethyl-, ethyl-, and diethylamine. The solid adsorbent tubes contained

two sections of 20/50 mesh Amberlite XAD-7 resin coated with 10# by weight

of the derivatizing reagent NBD chloride (7-chloro-4-nitrobenzo-2-oxa-1 ,3-

diazole). Air was pumped through the tubes at low flowrates using a personal sampling pump. The samples collected on the coated resin were prepared for analysis by transferring front and back sections to separate

vials, adding approximately 25 mg of sodium bicarbonate followed by 2.0 mL

of a 5# NBD chloride in tetrahydrofuran solution, shaking on a mechanical

shaker for 0.5 hour, and then heating at 60 °C in a hot water bath for 2.5

hours. The samples (and standards) were allowed to cool and then 15-pL aliquots were injected into a high performance liquid chromatograph with a fluorescence detector or a UV/visible wavelength detector for analysis. The

10
method described in this paper was tested at sample loadings equivalent to

air concentration ranges of 0.5 to 30 ppm for a sample volume of 10 L for

the four amines studied. The method was not affected by relative humidity

or by the presence of a combination of these amines in the same atmosphere.

[24] Goller, J. W.

Displacement of Polar by Non-Polar Organic Vapors in Sampling Systems

Am. Ind. Hyg. Assoc. J. 46, 170-173 (1985)

This paper describes a method for collecting vapor of toluene, xylene,

butanol, acetone, isopropanol, ethanol, and methanol and an analytical procedure to separate and determine the quantity of each compound. The

sampling train consisted of a personal sampling pump (three pump flow rates were used to collect different sample volumes) with two charcoal tubes in

series. Each of the tubes consisted of a front and a rear section; the

front section contained 100 mg of coconut based charcoal, and the rear sec- tion contained 50 mg of charcoal. The second tube collected vapors which

passed through the first tube by overloading or by selective displacement.

Carbon disulfide with 1% amyl alcohol was used to desorb the vapors from the

charcoal. The analysis was done by gas chromatography on a 1 0% FFAP with

80/100 mesh Chromosorb W, the detector was a flame ionization detector.

Each of the sections of the tubes was analyzed separately. The authors con- cluded that non-polar compounds will displace polar compounds in charcoal

sampling systems; competitive adsorption also occurs among polar compounds.

They also concluded that, when sampling air containing mixtures of organic

vapors of unknown concentrations, it may be helpful to use back-up tubes in case of breakthrough; also that the back-up should contain silica gel when

the mixture contains both polar (especially ethanol and methanol) and non- polar compounds.

[25] Gonzalez, J., and Levine, S. P. The development and Evaluation of a Thermally-Desorbable Miniature

Passive Dosimeter for the Monitoring of Organic Vapors

Am. Ind. Hyg. Assoc. J. 47, 339-346 (1986).

This paper describes the development and evaluation of a miniature passive

dosimeter for sequential monitoring of short-term exposure limits of organic

vapors and/or for the monitoring of low concentration levels of organic

vapors. The sampling medium was a fraction (5-mm diameter by 0.58-mm disk)

of the DuPont strip used in Pro-Tek organic vapor badges. The effects of

humidity, background air pollution, repeated re-use of sorbent, and transportation and storage of collected samples were investigated. The vapor

generator, dynamic exposure, and analysis system used was capable of shortperiod square concentration waves. Benzene was used as the test vapor.

Analysis of exposed samples was performed by thermal desorption and gas

chromatography. Factors included in laboratory evaluation of the monitor

were desorption, efficiency, capacity, sensitivity, accuracy and precision

concentration level, environmental conditions (e.g., air face velocity,

relative humidity), and sample stability during short and long periods of

time. The authors concluded that performance of the monitor was not affected by concentration level (in the range 0.1 to 50 ppm), relative

humidity up to 80%, and air face velocities of 40 to 100 fpm. The calculated overall system accuracy was 14% for the range 0.1 to 1 ppm, and 15%

for the range 1 to 50 ppm.

11
[26]

Heitbrink, W. A., and Crouse, W. E.

Application of Industrial Hygiene Air Sampling Data to the Evaluation

of Controls for Air Contaminants

Am. Ind. Hyg. Assoc. J. 45, 773-777 (1984)

In this paper, the following hypothesis is stated: "At an operation where

air contaminants are well-controlled, there should be no significant difference in concentration between the worker’s exposure, area samples collected near emission sources and background area samples collected away from

emission sources". The hypothesis requires the use of concentration differences to establish whether a control is effective and whether important

emission sources are being controlled. Stating this hypothesis as a null

hypothesis, statistical tests can be used to evaluate its validity. The

purpose of the paper is to discuss the application of the following statistical methods: analysis of variance, and Duncan’s Multiple Range Test.

[27]

Hunt, R. J., Neubauer, N. R., and Picone, R. F.

An Improved Procedure for Sampling and Analysis of Dinit rotoluene

Vapor Concentrations in Workplace Air

Am. Ind. Hyg. Assoc. J. 41, 592-594 (1980)

A method is described which combines collection of dinitrotoluene (DNT)

vapor onto silica gel sample tubes, desorption in chloroform, and gas chromatographic determination of the various isomers of dinitrotoluene. The

sampling tubes were commercially available. Injections of solutions of DNT

in chloroform were made into a GC glass column packed with 1.5% FFAP (Free

Fatty Acid Phase) on 60/80 mesh Chromosorb G (acid washed and dimethyldichlorosilanizedl. Concentrations of less than 10% of the Threshold Limit

Value (1.5 mg/rrn) for dinitrotoluene were determined in a 50-liter air

sample.

[28]

Hurley, G. F., and Ketcham, N. H.

A Solid Sorbent Personal Sampling Method for the Determination

of Acrolein in Air

Am. Ind. Hyg. Assoc. J. 39, 615-619 (1978)

This paper describes a personal air sampling method, using coated activated

carbon with subsequent analysis by gas chromatography, developed for the

analysis of acrolein in the 0.05 to 5 ppm range for 5-liter air samples.

The adsorbent chosen was activated carbon coated with a 5% ethanolic solution of hydroquinone, an acrolein polymerization inhibitor. Desorption of

acrolein from the sorbent was accomplished by addition of carbon to cooled

ethylene chloride, followed by a 30-minute contact with occasional shaking.

The chromatographic column packing was 9% Carborwax 20M-Terephthalic Acid on

40/60 mesh Chromosorb T. The detector was a flame ionization detector. The

peak height, or area, of the acrolein at 4.6 minutes retention time was

measured. The amount of acrolein present was determined from a calibration

standard or standard curve, this value was corrected by a previously determined desorption efficiency for the amount of acrolein present. The authors

concluded that a sensitivity of about 0.25 urn of acrolein per half mL of

solvent (0.02 ppm of acrolein for a 5-L air sample) was possible.

[29]

Jonas, L. A., Sansone, E. B., and Farris, T. S.

The Effect of Moisture on the Adsorption of Chloroform by Activated

Carbon

12
Am. Ind. Hyg. Assoc. J. 46, 20-23 (1985)

This paper reports a study of the effect of moisture on the ability of a granulated activated carbon to adsorb chloroform vapor from a flowing

airstream under three test conditions: (1) chloroform and water vapor were introduced concurrently into a dry carbon bed; (2) dry chloroform was introduced into a humidified carbon bed; and (3) humidified chloroform was introduced into a carbon bed at the same relative humidity. The criterion

for bed performance was 1 % breakthrough time, the time at which the ratio of

exit to inlet gas concentration was 0.01. Kinetic adsorption tests were carried out on a vapor adsorption test apparatus which was modified to permit the generation and subsequent mixing of up to three vapors

simultaneously. The vapors penetrating the bed were passed onto a gas

chromatograph glass column packed with 28% Pennwalt 223 + 4$ KOH on 80/100

mesh Gas Chrom R support. A flame ionization detector was used. For the~

tests, chloroform concentration was essentially constant at 108 _+ 2 mg/cnr,

relative humidity (RH) varied from 0 to 97%. The results indicated that,

for a dry carbon bed, the 1 % breakthrough time for chloroform adsorbed from

atmospheres of RH from 13% to 95% was essentially the same as that when RH = 0 %; for humidified carbon beds, no change in 1 % breakthrough time for

chloroform was observed until RH was >40%

[30] Kim, W. S., Geraci, C. L., Jr., and Kupel, R. E. Solid Sorbent Tube Sampling and Ion Chromatographic Analysis of

Formaldehyde

Am. Ind. Hyg. Assoc. J. 4l_, 334-339 (1980)

A new method for collection and analysis of atmospheric formaldehyde is discussed in this paper. The method is based on solid sorbent tube collection

and ion chromatographic analysis. Ion chromatography consists of ionexchange chromatography, background ion suppression, and conduct imetric

detection. The solid sorbent tube was prepared with two sections of impregnated charcoal separated by silylated glass wool. The proprietary

impregnating material converts formaldehyde to formate. After the sampling,

at either 50 cc/min or 200 cc/min, each section of the charcoal was placed

in separate centrifuge tubes; 10.0 mL of 0.1% H^Op solution was added to the

adsorbent section and 5.0 mL was added to the backup section. Then, after 1 hour of occasional shaking, each sample was placed in an ultra-sonic bath

for 20 minutes. After filtration through a mixed cellulose ester filter, a fraction of filtrate was injected into the anion system of an ion

chromatograph. The overall recovery of laboratory generated samples was

100% with 11% relative standard deviation.

[31] Krasnec, J. P., and Demaray, D. E. Instrumentation for Source Sampling and Characterization of Indoor and

Industrial Gaseous Pollutants

Presented at the Joint PNWIS/CPANS-APCA Annual Meeting, Calgary,

Alberta, Canada, Nov. 1

_

1 5 , 1985.

In this paper, sampling instrumentation design criteria for indoor/

industrial air pollution monitoring are presented. Grab samplers, passive

samplers, personal samplers, single-use devices, in-si tu measurement instruments, and microcomputer-controlled syringe and adsorbent tube samplers are compared. Recently introduced passive samplers and sequential grab samplers

13
are described in detail, their use for sampling of toxic organic pollutants

is highlighted.

[32] Krasnec, J. P., Demaray, D. E., Lamb, B., and Benner, R.

An Automated Sequential Syringe Sampler for Atmospheric Tracer

Studies

J. Atmos. Ocean. Technol. J_, 372-378 (1984)

The design and operation of an automated, sequential syringe sampler are described in this paper. The latest version included an advanced timing

system and collected 12 sequential time-averaged air samples, a rack and

pinion drive and a stepper motor provided the mechanical actuation of each

syringe. A crystal-controlled oscillator, which could be preset to a variable 2-to-8 minute interval, provided the time-base. Per syringe sampling

interval could be preset to give sampling times ranging from 2 to 120

minutes, permitting a total sampling time of up to 24 hours for the twelvestation sampler.

[33] Kring, E. V., Damrell, D. J., Basilio, A. N., Jr., McGibney, P. D.,

Douglas, J. J., Henry, T. T., and Ansul, G. R.

Laboratory Validation and Field Verification of a New Passive Air

Monitoring Badge for Sampling Ethylene Oxide in Air

Am. Ind. Hyg. Assoc. J. 45, 697-707 (1984)

A new diffusion colorimetric air monitoring badge for sampling ethylene

oxide is described in this paper. The badge was laboratory validated over

the range 4-375 ppm-hours. The reagent pack was removed from the badge

holder after exposure and analysis was performed on 1.0 mL of the absorbing

solution. The overall sampling and analysis accuracy of the badge was _+ 13.5%. The badge agreed very well, in 21 separate tests, with the most

widely used pump/charcoal tube method for sampling ethylene oxide in industrial workplace environments.

[34] Kring, E. V., Ansul, G. R., Basilio, A. N., Jr., McGibney, P. D.,

Stephens, J. S., and O’Dell, H. L.

Sampling for Formaldehyde in Workplace and Ambient Air Environments-Additional Laboratory Validation and Field Verification of

a Passive Air Monitoring Device Compared with Conventional

Sampling Methods.

Am. Ind. Hyg. Assoc. J. 45, 318-324 (1984)

This paper presents: (1) additional laboratory validation work on a new diffusional badge (see [33]) designed for colorimetric analysis and broad

sampling range; (2) field verification tests, and (3) some observations on

the most widely used (then) independent method, NIOSH P&CAM 125. Four independent sampling methods were used in all laboratory studies: the

pump/impinger sampling method, NIOSH P&CAM 125; the pump silica gel tube

monitoring method; the CEA Model 555 monitor; and the Lion Formaldemeter.

The field test protocol was based on NIOSH sampling strategy, a verification

plan developed jointly with the Ethylene Oxide Industry Council and past

experience. Laboratory validation tests confirmed an overall accuracy of

9.6 to _+ 11.555 for the badge over the exposure range of 0.12-6.8 ppm.

Laboratory test data also showed that the badge met NIOSH and OSHA accuracy

requirements of _< _+ 2555 down to 1 .6 ppm-hours (200 ppb) for an 8-hour TWA

exposure, was capable of accurately sampling for 15-minute exposures, and

14
was not affected by pressure or relative humidity variations. Results of

field tests at three different plant sites showed the badge to have excellent correlation with three commonly used methods for monitoring

formaldehyde.

[35] Kring, E. V., Ansul, G. D., Henry, T. J., Morello, J. A.,

Dixon, S. W. , Vasta, J. F., and Hemingway, R. E.

Evaluation of the Standard NIOSH Type Charcoal Tube Sampling Method for

Organic Vapors in Air

Am. Ind. Hyg. Assoc. J. 45, 250-259 (1984)

This paper reports on a study in which standard commercially-available

NIOSH-type charcoal tubes were used as an independent check on the con- centration in dynamic exposure chambers. Tests were conducted for 67 hours

at 80% relative humidity to simulate the worst conditions for industrial TWA

monitoring. Charcoal tube flow rates were controlled at 50 cnr /min. All

desorbed samples were analyzed on a gas chromatograph equipped with a flame

ionization detector and automatic liquid sampler. An improved protocol was used to test a number of the more common organic airborne contaminants; 14

of the 22 compounds failed to meet NIOSH accuracy requirements, suggesting

to the authors that workers in the industrial hygiene field should consider

the charcoal tube method only as an independent method and not as a primary

standard for air monitoring. The authors concluded that laboratory test

data indicated that the NIOSH charcoal tube sampling method has serious

deficiencies when used to determine the true exposure concentrations of many common industrial organic compounds in moist air, and they strongly recan- mended laboratory validation of charcoal tubes prior to field sampling.

[ 36 ] Kropscott, B. E., Coyne, L. B., Campbell, R. A., Kastl, P. E., and

Sowle, W. F., Ill

Robotic Applications Within Dow’s Health and Environmental Sciences

Laboratory

In Advances in Laboratory Automation Robotics 1985, Strimaitis,

J. R., and Hawk, G. L., eds. (Zymark Corp., Hopkinton, MA, 1985)

pp. 131-147

This paper presents two examples of automated sample preparation using a laboratory automation system (robot): (1) sample preparation and method optimization for subsequent chromatographic analysis; (2) whole tube

desorption, a new technique for analyte desorption from charcoal tubes in

industrial hygiene surveys. Sample extracts were analyzed using a gas

chromatograph equipped with an electron capture detector and a flame ionization detector. A data system was used to integrate peak areas and determine

concentrations from external standard calculations. The automated whole

tube desorption method avoided removal of the charcoal sorbent from the

glass sampling tube by desorbing the entire air sampling tube with chilled

solvent inside a test tube. The recovery of spiked samples desorbed using

the whole tube desorption method was similar to that for spiked samples

desorbed using a validated industrial hygiene monitoring method, which re- quired the removal of the sorbent prior to desorption. The authors

concluded that the laboratory automation system provided the accuracy,

precision, and reliability to automate and optimize the feed extractions;

that whole tube desorption had been developed as a viable means of desorbing

analytes from charcoal tubes; and that laboratory robots should not be

thought of as a replacement of the analyst.

15
[37] Krost, K. J., Pellizzari, E. D., Walburn, S. G., and Hubbard, S. A.

Collection and Analysis of Hazardous Organic Emissions

Anal. Chem. 54, 810-817 (1982)

The primary goal of the research program described in this paper was to

develop methodology for the reliable and accurate collection and analysis of

hazardous vapors present simultaneously in the atmosphere down to nanogram

per cubic meter amounts. This paper summarizes the overall progress made on

the development of an analysis system encompassing the collection and con- centration of organic pollutants from ambient air using tubes packed with

polymeric beads. After sampling, the cartridges were thermally heated under

a helium flow, the compounds desorbed, cryofocused, and subsequently introduced into a high-resolution glass or fused capillary for characterization

and measurement by gas chromatography/mass spectrometry /computer techniques.

Cartridges used to concentrate organic vapors consisted of a 1.5 cm x 6.0 cm bed of Tenax-GC (35/60); two or three cartridges were designated as blanks

for assessing occurrence of contamination. Thermal desorption of sampling

cartridges was accomplished by passing helium through the cartridge in a preheated (ca. 270 °C) chamber for 8 minutes at a flowrate of about 15

mL/min, into a liquid-nitrogen-cooled nickel capillary trap.

[38] Langhorst, M. L.

Monitoring Airborne Reactive Chemicals by Derivatization and High

Performance Thin Layer Chromatography-Anhydrides, Acid Halides,

Isocyanates

Am. Ind. Hyg. Assoc. J. 46, 236-243 (1985)

This paper discusses work on a versatile reagent-coated solid sorbent tube

developed for monitoring airborne reactive chemicals including acetic an- hydride (AcAn), chloroacetyl chloride (CAC), and isocyanatoethyl methacrylate (IEM) . Since all three of these chemicals react readily with reac- tive hydrogens, e.g., water vapor, amines, and primary alcohols, long-term

collection without derivatization is precluded. The air sampling sorbent

was 120/140 mesh GLC-110; the derivatizing agent was 0 . 20% 1 -(2-pyridyl)

piperazine. After collection of the sample, the sorbent from each tube was desorbed in two mL of hexane (five mL for acetic anhydride tubes), shaken

for five minutes on a mechanical shaker, and analyzed by high performance

thin layer chromatography. The concentration of AcAn, CAC, or IEM in the

original air was calculated against external standards. The recoveries for

AcAn, CAC, and IEM were 91 . 5 %, 95 . 2%, and 85.0%, respectively. Humidity effects, storage effects, and potential interferences were also evaluated.

[39] Levine, S. P., Gonzalez, J. A., and Kring, E. V.

A Dynamic Vapor Exposure System for Evaluating Passive Dosimeters

Am. Ind. Hyg. Assoc. J. 47, 347-353 (1986)

The design and validation of a dynamic vapor exposure system for the evaluation of passive dosimeters (see [46]) for ceiling exposure monitoring of low

concentration levels are reported in this paper. The test vapor generator

consisted of a thermally regulated diffusion tube assembly, a dilution air

cleaning device, flow regulating and humidifying assembly, a mixing chamber,

rotameters for flow rate monitoring, and associated tubing. The generator

vapor (benzene) passed through a mixing chamber into the exposure chamber.

The exposure chamber concentration was determined by two independent in-situ

instruments: (1) a real-time total hydrocarbon monitor (photoionization

16
detector) calibrated against a test mixture traceable to National Bureau of

Standards primary standards; and (2) a near-real-time monitor (gas

chromatograph, GC, with a flame ionization detector) calibrated against liquid standards and vapor primary standards. The concentration profiles were

found to be highly reproducible and accurate to the 0.1 -ppm level (sample

loadings of 10 ng benzene per sample). The authors concluded that the system yielded results with a high accuracy and precision over a wide range of

benzene concentration (0.1 to 50 ppm) and exposure time (5 to 30 min).

Significant features of the system included a combined inlet system for the

thermal desorption of passive dosimeters and the direct injection of vapors

and liquids, and the use of iso-octane as a solvent for benzene for liquid

calibration of the GC at very low levels.

[40] Mason, D. W. , Dillon, H. K., and Glaser, R. A.

Sampling and Analytical Methods for the Determination of

Monochloroacetic Acid in Air

Am. Ind. Hyg. Assoc. 47, 14-21 (1986)

The development and validation of a sampling and analytical method for the

determination of monochloroacetic acid (MCA) vapor in workplace air are described in this paper. Collection on silica gel and collection on a reactive, impregnated filter (sodium bicarbonate on quartz fiber) were

considered. MCA was desorbed from both types of collection media with

reagent grade distilled deionized water; ion chromatography was used to

determine the monochloroacetic anion. The sorbent tubes contained silica

gel (20/40 mesh), divided into a 100-mg sorbing section and a 50-mg back-up

section. The impregnated filters consisted of quartz filter disks with a 5-

ym pore size, which had been soaked in a saturated solution of sodium

bicarbonate and then dried under vacuum. A continuous monitor was employed

as an independent or reference sampling and analytical method. It was found

necessary to add the silica gel solid sorbent to an aqueous solution of MCA

because ions extracted from the sorbent affected the base line of the ion

chromatographic response near the monochloroacetate peak. A more complex

procedure was required for the reactive filters, to remove excess bicarbonate ion from the solution prior to analysis. The silica gel was deemed,

from test results, to be more acceptable than the reactive filter for sam- pling MCA in air. Collection of MCA on the reactive filter showed

considerable promise, however, the method was not validated because

refrigeration of exposed filters or extraction of filters soon after ex- posure was necessary to preserve the MCA for subsequent determination. The

silica gel method was validated in the concentration range of 0.35 to 29

mg/nr in 3

- L air samples, the capacity of the silica gel was in the range of

3 to 4 mg of MCA per 100 mg of sorbent. There were no significant interferences from glycolic acid, acetic acid, dichloroacetic acid,

trichloroacetic acid, fluoride and chloride compounds, or water vapor; effects on analytical data due to variations in temperature and humidity of

the test atmosphere, sample storage time, and chromatographic parameters

were found to be minimal.

[41] Melcher, R. G. , Borders, R. A., and Coyne, L. B.

Development and Validation of Personal Monitoring Methods for Low

Levels of Acrylonitrile in Workplace Atmosphere: I. Test

Atmosphere Generation and Solvent Desorption Methods

Am. Ind. Hyg. Assoc. J. 47_, 152-157 (1986)

17
The purpose of the study reported in this paper was to optimize monitoring

methods and to investigate new technology for the determination of low

levels of acrylonitrile (0.05 to 5 ppm) in workplace atmospheres. A dynamic

atmosphere generation method was developed in the first phase of the study;

in the second phase, various potential sorbents were investigated and com- pared in a laboratory validation study. Carbosieve B, Ambersorb XE-340,

Ambersorb XE-347, Ambersorb XE-348, and three volumes of Pittsburgh CoconutBase (PittCB) activated charcoal were the candidate sorbents. The sorbents

were desorbed by pouring into 10 mL of dry-ice-chilled carbon disulfide or

2% acetone in carbon disulfide and shaking for 30 minutes. The extracts

were analyzed by gas chromatography with flame ionization detection (FID) or

a nitrogen selective detector (PND); the limit of detection for

acrylonitrile was 4yg/10mL and 0.2 yg/10 mL for PND, based on a 3 to 1 signal-to-noise ratio. A collection tube containing 600 mg of PittCB charcoal was optimum for sampling for a full 8-hour shift. Ambersorb XE-348 was

found to be a better sorbent for acrylonitrile and less affected by

humidity. The best adsorption solvent was found to be carbon disulfide plus

2% acetone; recoveries near 90% were obtained for both the tubes containing

charcoal and Ambersorb. The PND was found to be more sensitive and more selective than the FID.

[42] Moore, G. , Steinle, S., and Lefebre, H.

Theory and Practice in the Development of a Multisorbent Passive

Dosimeter System

Am. Ind. Hyg. Assoc. J. 45, 145-153 (1984)

A new family of passive dosimeters was fabricated to allow the use of multiple sorbents and analytical techniques suited to a wide range of sampling

situations. Sorbent capsules were designed both for conventional solvent

desorption and to be used with a newly developed rapid thermal desorber

capable of automation for multiple samples. This paper describes the

development of the system together with laboratory tests and results and the

effects of environmental parameters. The paper deals principally with work

on solid sorbent systems.

[43] Morris, C., Berkley, R., and Bumgarner, J.

Preparation of Multicomponent Volatile Organic Standards Using

Static Dilution Bottles

Analytical Letters 16 (A20), 1585-1593 (1983)

This paper discusses a static dilution bottle designed to prepare multicomponent volatile organic standards, in helium. Different concentrations may

be obtained by using different sized bottles, by adjusting the component

amounts introduced into the bottles, or by varying the amount of vapor

removed by gas-tight syringes for injection into an analytical instrument

such as a gas chromatograph/mass spectrometer or into a solid adsorbent

sample collection cartridge. Mixtures of up to 35 compounds, each having a vapor pressure greater than 1 Torr at 20 °C, were prepared and applied for

one week with no loss of precision. The procedure offers flexibility in

producing calibration curves and preparing quality assurance standards.

[44] Pankow, J. F., and Kristensen, T. J.

Effects of Flow-Rate and Temperature on Thermal Desorbability of

Polycyclic Aromatic Hydrocarbons and Pesticides from Tenax-GC

Anal. Chem. 55, 2187-2192 (1983)

18
The purpose of the research described in this paper was to investigate the

desorbability of a set of compounds which were generally not considered to

be easily thermally desorbable from Tenax-GC. A main objective was to investigate the extent to which increasing the carrier flow rate could be used

to accomplish a quantitative transfer to a fused silica capillary column at

minimal desorption temperatures while maintaining high resolution in the

subsequent chromatographic run. Polynuclear aromatic hydrocarbons larger

than benz[ a] -anthracene were studied. The desorbabilities of the compounds

were investigated as a function of helium carrier gas flow rate and desorption temperatures; other carrier gases of larger molecular sizes were also

investigated. The desorption apparatus consisted of a cartridge packed with

0.110 g of 35/60 mesh Tenax-GC, with an injection septum mounted on the top

end and with the bottom end interfaced to a capillary column. Each experiment consisted of loading 4.0 yL of the standard on the top of the cartridge

followed by a series of eight 20-min desorptions and eight accompanying

runs. At the same volume flow rate, carbon dioxide, methane, ethene, and

propane were not found to give more facile desorption than helium for the

study compounds. The desorbing compounds were trapped on a fused silica

capillary column at -30 °C. Excellent resolution and separation number performance was maintained despite the use of high desorption carrier gas flow

rates.

[45] Pellizzari, E. D., and Krost, K. J.

Chemical Transformations during Ambient Air Sampling for Organic

Vapors

Anal. Chem. 56, 1813-1819 (1984)

The subject of this paper is a study of potential halogenation, nitrosation,

and ozonization reactions and their inhibition with sodium thiosulfate

during the collection of vapor-phase organics from ambient air. The re- search centered on a sorbent collection method using Tenax-GC. A thermal

desorption capillary gas chromatography /mass spectrometry (GC/MS) method was

used to analyze analytes collected on a Tenax-GC sampling cartridge. Field

in situ reaction studies were conducted by sampling ambient air using TenaxGC cartridges and Tenax-GC cartridges spiked with deuterated compounds;

subsequently the cartridges were analyzed to identify deuterated compounds.

The use of styrene-dg and cyclohexene-d^ spiked sampling devices and GC/MS

analysis allowed the°detection and identification of several deuterated

oxidation and halogenated products. Oxidation was prevented when filters

employed for removing particulates were impregnated with 5-10 mg of sodium

thiosulfate and placed in front of the sorbent cartridge; halogenation reac- tions were also considerably reduced.

[46] Pellizzari, E. D., Demian, B., and Krost, K. J.

Sampling of Organic Compounds in the Presence of Reactive Organic

Gases with Tenax-GC

Anal. Chem. 56, 793-798 (1984)

The testing of the Tenax-GC sampling cartridge to gain insight into potential reaction problems which may be encountered during field sampling is

reported in this paper. The sampling of vapor-phase organics in the

presence of reactive inorganic gases with the Tenax-GC sampling cartridge

was statistically evaluated. Laboratory air containing oxidants for sam- pling was synthesized. A thermal desorption capillary gas chromato19
graphy/mass spectrometry method was used for qualitative analysis of TenaxGC or analyte degradation products. Experimental results clearly

demonstrated that the presence of oxidants in ambient air could produce

decomposition products both from the Tenax-GC sorbent and from analytes adsorbed to the adsorbent. Removal of oxidants prior to the capture of

organic vapors was investigated by use of mild reducing agents impregnated

in filters for particulate. Sodium-thiosulfate-impregnated glass fiber and

Teflon filters quantitatively decomposed ozone.

[47] Pellizzari, E. D., Bunch, J. E., Berkley, R. E., and McRae, J.

Collection and Analysis of Trace Organic Vapor Pollutants in Ambient

Atmospheres. The Performance of a Tenax GC Cartridge Sampler for

Hazardous Vapors.

Analytical Letters 9_ (1), 45-63 (1976)

This paper reports on the evaluation of several sorbents as collection media

for the quantitative concentration and analysis of volatile, hazardous,

vapor-phase compounds from ambient atmospheres under a variety of conditions

relevant to field sampling. The sorbents evaluated were graphitized carbon,

PBL carbon, PCB carbon, SAL9190, M180B, Tenax-GC (35/60 mesh), Porapak Q

(100/120 mesh), Chromosorb 101 (60/80 mesh), Chromosorb-1 02 (60/80 mesh),

Chromosorb 104E (60/80 mesh). Tenax-GC was selected as the best available

sorbent for general use because of its wide range of applicability, its

thermal stability, and its low retentive index for water.

[48] Pellizzari, E. D., Gutknecht, W. F., Cooper, S., and Hardison, D.

Evaluation of Sampling Methods for Gaseous Atmospheric Samples

U.S. Environmental Protection Agency, Final Report on Contract

No. 68-02-2991

This report describes a research program conducted to test and evaluate

several alternatives for collecting and transferring samples to the

laboratory for the analysis of a variety of toxic organic pollutants by gas

chromatography. Sample storage media included three types of polymeric

bags, glass bulbs, electropolished and Summa polished canisters, Tenax-GC

and charcoal cartridges, and nickel cryogenic traps. The storage media were

tested using 27 compounds including hydrocarbons, aromatics, halogenated

hydrocarbons, halogenated aromatics, and oxygen-, nitrogen-, and sulfurcontaining compounds. Quantitative laboratory stability tests were conducted for 1 5% of the compounds over a 7-day storage period. The potential effect of inorganic gases as interferences during the collection of

test compounds was quantitatively studies. An automatic two-channel ambient

air sampler using sorbent cartridges as the collection media was designed

and fabricated. A quality control and quality assurance program was established and maintained for all measured and analyzed data.

[49] Persoff, P., and Hodgson, A. T.

Correction for External Mass-Transfer Resistance in Diffusive

Sampling

Am. Ind. Hyg. Assoc. J. 46_, 648-652 (1985)

In this paper, the authors expanded on the hypothesis of Tompkins and

Goldsmith that depletion around the opening of a sampler occurs when external mass transfer resistance is significant compared with internal mass transfer resistance, and they demonstrated experimentally a simple method to

20
correct for errors in diffusive sampling due to external mass transfer

resistance. A diffusive sampler for water vapor was used to demonstrate the

method of correction for external mass transfer resistance, the water vapor

sampler used molecular sieve as the sorbent. Extrapolated concentrations of

water vapor were compared with concentrations measured with a dew-point

hygrometer. It was demonstrated that the effect of external mass transfer

resistance in reducing the collection efficiency of diffusive samplers was

not dependent on the analyte being sampled or the sorbent; the effect was observed for SO^, NOp, and water vapor uptake, with three different sorbents

for water vapor (molecular sieve, concentrated H^SO^, and silica gel).

[50] Popendorf, W.

Vapor Pressure and Solvent Vapor Hazards

Am. Ind. Hyg. Assoc. J. 45, 719-726 (1984)

This paper discussed applications of vapor pressure to industrial hygiene

and outlines the importance of vapor pressure as it affects airborne con- centration and vapor hazard. The terms Vapor Hazard Ratio and its common

logarithm, the Vapor Hazard Index (VHI), were introduced as the ratio of the

physical concentration at the source (vapor pressure equivalent) to the ac- ceptable concentration in the breathing zone. The VHI was claimed to

provide a practical tool to predict the relative hazard of vapor concentrations of different solvents used in similar settings, to quantitatively

evaluate or design ventilation systems, to improve a hazard rating or hazard

communication system, or to influence environmental sampling strategies.

[51] Russwurm, G. M., Stikeleather, J. A., Killough, P. M., and

Windsor, J. G., Jr.

Design of a Sampling Cartridge for the Collection of Organic Vapors

Atmospheric Environment 15, 929-931 (1981)

In order to prevent inadvertent contamination of cleaned Tenax by improper

handling, a new sampling cartridge was designed. The design, manufacturing

procedure, and preliminary test results are given in this paper. The

cartridge incorporates the standard glass sampling tube that seals the sor- bent tube from external contamination. The Tenax-filled tube and sampling

cartridge were assembled in a clean laboratory area, the sealing was checked

by pressurizing the cartridge with prepurified nitrogen and monitoring the

pressure. The cartridge was then brought to a positive pressure of 1 atmosphere and stored; as needed, the sampling cartridges were taken to the field

in a pressurized condition.

[52] Samimi , B., and Falbo, L.

Comparison of Standard Charcoal Tubes with Abcor (NMS) Gasbadges

within Controlled Atmosphere

Am. Ind. Hyg. Assoc. J. 46_, 49-52 (1985)

In the effort reported in this paper, charcoal tubes were compared with

Abcor (NMS) Gasbadges under controlled conditions within an inhalation chamber equipped with a dynamic air flow system. A calibrated infrared gas

analyzer was used to monitor the concentration of organic solvent con- tinuously throughout the experiments. The organic compounds used in the

experiments were styrene, ethyl acrylate, and N-butyl acrylate. Samples

were collected on 133 badges and 102 charcoal tubes under two different air

velocities of 0.22 m/sec and 0.44 m/sec. The results of the study suggest

21
that prevailing air currents at the workplace should be regarded as a con- tributing factor to the rate of sample collection on passive dosimeters.

[53] Senum, G. I. Theoretical Collection Efficiencies of Adsorbent Samplers

Environ. Sci. Technol. 1_5, 1073-1075 (1981)

This paper is a theoretical discussion of collection efficiencies of adsorbent samplers and, in particular, of breakthrough volume. Chromatographic

response theory is applied to adsorption samplers and a breakthrough volume

is defined and explicitly expressed in terms of a required collection efficiency, the retention volume for the adsorbate/absorbent combination, and

the number of theoretical plates of the adsorbent. The breakthrough volumes

derived in this paper are claimed to be exact for all N (number of theoretical plates of the adsorbent) since no approximations are involved.

[54] Spee, T.

Evaluation of an ISO Draft Proposal for Sampling and Analysis of

Chlorinated Hydrocarbon Solvent Vapors in Workplace Atmospheres

Am. Ind. Hyg. Assoc. J. 47, 27-36 (1986)

This paper reports on the evaluation of an ISO draft proposal for sampling

and analysis of chlorinated hydrocarbon solvent vapors in workplace atmospheres, by means of a round- robin test. The repeatability and

reproducibility for the determination of tetrachlorome thane, trichloromethane, t richloroethane , 1,1,1- trichloroethene, and tetrachlorethene were ascertained at three concentration levels; also, parameters such as breakthrough and loss on storage were determined. Samples were taken by 11 participants from 6 countries. The method described by the draft proposal

is a pumped charcoal tube-solvent desorption gas chromatographic method.

The collected organic vapors were desorbed by a suitable solvent and

analyzed by means of a gas chromatograph with a flame ionization detector

(FID). The author concluded that improvements in the method are necessary

for the determination of tetrachloromethane and trichloromethane, that the

method is sufficient for the other three compounds, and that a possible improvement of the method would be the prescription of an electron capture

detector instead of an FID for compounds with a low FID sensitivity and low

MAC values.

[55] Stockton, S. D., and Underhill, D. W.

Field Evaluation of Passive Organic Vapor Samplers

Am. Ind. Hyg. Assoc. J. 46, 526-531 (1985)

This paper reports on the evaluation of the performance of passive diffusion

organic samplers manufactured by 5 companies and charcoal tubes manufactured

by one company, in an industrial atmosphere known to contain vapor phase

concentrations of benzene, toluene, and xylene. Six samplers of each type

(36 in all) were exposed to essentially the same atmosphere. The collected

organic vapor was desorbed by carbon disulfide and analyzed on a gas

chromatograph with a flame ionization detector. The analytical results were treated with two-way analysis of variance, and the least significant difference test was applied to the mean values to further refine the data. The

author concluded that each type of sampler could be used for industrial

hygiene evaluations with confidence.

22
[56] Underhill, D. W.

Efficiency of Passive Sampling by Adsorbents

Am. Ind. Hyg. Assoc. J. 45, 306-310 (1984)

It was the purpose of this paper to show how interactions between the

sampled contaminant and the adsorbent (usually charcoal) affect the sampling

efficiency and thereby prevent reversibility of diffusion in passive

sampling. The effects of the interactions are reflected in the adsorption

isotherm. Calculations of sampling efficiency were made in terms of dimensionless variables for adsorption controlled by the Langmuir, Freundlich,

and Dubinin-Radushkevich (D-R) isotherms, three common nonlinear isotherms.

Of particular interest were the results calculated from the D-R isotherm,

since it had been shown that this isotherm could accurately describe the adsorption of hydrocarbons and many related compounds on activated charcoal.

The author concludes that 1) the effectiveness of a passive dosimeter

depends strongly on the adsorption isotherm, 2) the D-R isotherm is consistent with high sampling efficiency, and 3) the isotherms giving high

sampling efficiency are also consistent with the retention of adsorbate for

extended periods of time.

[57] Vasta, J. F., and Kvartek, E. J.

Development of a Sampling and Analytical Method for the Insecticide

Propoxur

Am. Ind. Hyg. Assoc. J. 46, 230-232 (1985)

In this paper, a method for the collection and analysis of airborne propoxur

(2-(1-Methylethoxy) phenol methylcarbamate) is described. Sorbent tubes for

sampling consisted of glass tubes packed with *[ 0)% Carbowax 400 supported on 80/100 mesh Supelcoport. The propoxur was desorbed by methanol and the ex- tract was analyzed by high pressure liquid chromatography. The method was developed to collect low levels, about 0.1 ppb, of propoxur in air; the

limit of detection of the analytical method was one yg per sample.

Recoveries of greater than 87% were obtained from control samples evaluated

at 0.5 and 1 .0 mg.

[58] Wallace, L. A., Pellizzari, E. D., Hartwell, T. D., Sparacino, C. M.

,

Sheldon, L. S., and Zelon, H.

Personal Exposures, Indoor-Outdoor Relationships, and Breath Levels of

Toxic Air Pollutants Measured for 355 Persons in New Jersey

Atmos. Environ. ]j), 1651-1661 (1985)

The measurement methods and results for a second phase of E.P.A.’s Total

Exposure Assessment Methodology Study are reported in this paper. Twenty

toxic, carcinogenic, or mutagenic organic compounds were measured in the air

and drinking water of 355 participants. Each participant carried a personal

sampler during normal daily activities for two consecutive 12-hour periods

(one participant residing in each of 100 areas had an identical sampler

operating in the back yard for the same two 12-hour periods). All participants also collected two drinking water samples. Personal and outdoor

air samples were collected for 12-hour periods on cartridges containing

about 2 g of 40/60 mesh purified Tenax. The cartridges were analyzed by

thermal desorption and cryofocussing of the organic vapors followed by

capillary gas chromatography/mass spectrometry/computer analysis. About

3000 samples were collected, of which 1000 were quality control samples.

23
[59] Wallace, L. A., Pellizzari, E. D., Hartwell, T., Rosenzweig, M.,

Erickson, M. D., Sparacino, C. M. , and Zelon, H.

Personal Exposure to Volatile Organic Compounds; I. Direct

Measurements in Breathing Zone Air, Drinking Water, Food, and Exhaled

Breath

Environ. Res. 35, 293-319 ( 1984)

This paper reports on a pilot study to test methods of estimating personal

exposures to 20 target toxic substances and corresponding body burdens. One

of the objectives of the volatile organics portion of the study was to test

a personal monitor employing Tenax-GC adsorbent to collect selected organic

compounds from breathing-zone air for 5-10 hours. The target compounds were selected on the basis of their extensive use and likely toxicity. All air

exposures were measured using personal air quality monitors. All volatile

organics except vinyl chloride were collected using glass tubes containing

1.5 g of Tenax-GC adsorbent. Samples were analyzed using thermal desorption

and purging by helium into a liquid-nitrogen-cooled nickel capillary

cryogenic trap, followed by high resolution glass column gas

chromatography /mass spectrometry techniques. Vinyl chloride was collected

using a dimethyls ili cone rubber permeable membrane badge, the activated

charcoal element was desorbed by carbon disulfide and the eluent analyzed

using a gas chromatograph with electron capture detection. About 230 personal air samples, 170 drinking water samples, 66 breath samples, and 4 food

samples were analyzed for the target chemicals.

[60] Walling, J. F., Bumgarner, J. E., Driscoll, D. J., Morris, C. M.,

Riley, A. E., and Wright, L. H.

Apparent Reaction Products Desorbed From Tenax Used to Sample Ambient

Air

Atmos. Environ. 20, 51-57 (1986)

This paper reports on the collection of ambient air samples using distributed air volume sets (see [61]) of tandem Tenax-GC beds. The

distributed air volume sampling approach requires simultaneous collection of

several samples, each at a very different flow rate. Many interfering

processes scale nonlinearly with volume sampled; if they are important, apparent atmospheric concentrations become dependent on the volume sampled.

This sampling approach does not permit identification or enumeration of

interferences; however, the inclusion of tandem (two in series) beds and/or

presampling spikes of deuterated species can assist in identifying adsorbate

loss through inadequate retention. Tenax-GC of differing and uncontrolled

histories was solvent-cleaned, desorbed, and packed in cartridges containing

1.2-g beds. Fifty-seven organic compounds, principally aromatic and

halogenated hydrocarbons, were used. After sampling, the Tenax-GC was thermally desorbed and the eluent cryofocussed on a glass capillary in a gas

chromatograph/mass spectrometer. Detection limits were between 1 and 3 ng.

Inconsistent sets of apparent concentrations not due to contamination,

operating errors, or blanks were often observed. Unidentified chemical

reactions during sampling and/or thermal desorption were implicated. The

authors concluded that, for aromatic and halogenated hydrocarbons, an em- pirical evaluation of data from each sampling situation using distributed

air volume sets seemed necessary.

[61 ] Walling, J. F.

The Utility of Distributed Air Volume Sets When Sampling Ambient

24
Air Using Solid Adsorbents

Atmos. Environ. _18.» 855-859 (1984)

The distributed air volume sampling approach (see [60]) is illustrated in

this paper by the use of Tenax-GC as the adsorbent. More than 100 peaks are typically observed in chromatograms of materials adsorbed from air and thermally desorbed from Tenax-GC. Quantitative interpretation of the data was complicated by the possible existence of at least three factors: 1) exceeding the capacity of the adsorbent; 2) inadequate blank corrections; 3)

reactions usually called "artifact formation". Any substance removed from

an adsorbent could be an atmospheric constituent or the result of reactions

occurring during sampling or desorption. The underlying idea of the distributed air volume sampling approach is that at any fixed sampling rate the

amount of a substance adsorbed will be a linear function of the volume

sampled. Lack of dependence on volume is presumptive evidence that the

results describe the atmosphere sampled, any artifact reaction which does

not scale linearly with volume sampled should be revealed by the approach.

Cleaned virgin Tenax-GC was packed into stainless steel sampling tubes.

Analysis was by thermal desorption into a capillary gas chromatograph with mass spectrometric detection; analysis was confined to a set of 34 specific

substances, principally aromatic and halogenated hydrocarbons. Sampling

times ranged from 3 to 4 hours. Two different sampling-volume ranges were

used, the initial arbitrary judgment was that the ratio of the largest to

smallest volume sampled in each set should be about 5. The author concluded

that because a distributed air volume set can reveal several kinds of behavior not correctly dependent on air volume, it is more useful for

discovering difficulty in data than the conventional tandem bed approach and

is just as practical to implement.

[62] Walling, J. F., Berkley, R. E., Swanson, D. H., and Toth, F. J.

Sampling Air for Gaseous Organic Chemicals Using Solid Adsorbents.

Application to Tenax

U.S. Environmental Protection Agency, Research and Development, Project

Summary, EP-600/S4-82-059 , December, 1982

This paper describes a simple input-output model for a two-phase flow system

with fixed bed and its application to Tenax adsorption of atmospheric

contaminants. The objectives of the work were: 1) to obtain a simple alternative model (applicable to field sampling with solid adsorbents) to

standard chromatographic theory; 2) to test the accuracy of the function obtained in describing a few simplified controlled laboratory experiments; 3)

to design a simple practical scheme for sampling and data interpretation

which also could provide evidence of consistency in the results. The

utility of the model was tested by simulated sampling using a permeation

tube system to supply known concentrations of cleaned pollutant-doped air at

various flow rates. Flame ionization detection of the output of the Tenax

cartridge was utilized. Agreement of computed retention volumes with published values was generally within _+ 25 percent. The authors concluded that

the model is capable of giving a reasonable and compact description of the

sampling behavior of the Tenax cartridges over a range of variables likely

to be met in the field. A suggested simplified approach for routine sam- pling is presented.

[63] Werner, M. D.

The Effects of Relative Humidity on the Vapor Phase Adsorption of

25
Trichlorethylene by Activated Carbon

Am. Ind. Hyg. Assoc. J. 46, 585-590 (1985)

The purposes of this paper were: 1) to present results which illustrated

the degree to which several levels of relative humidity reduced the adsorption capacity of activated carbon for a single volatile organic compound,

trichloroethylene (TCE) , at low influent concentrations; 2) to examine the

interaction between TCE concentration and humidity during adsorption on carbon; 3) to suggest a potential approach that may be taken for predicting

the degree of impact of relative humidity on the adsorption process.

Experimental trials were performed at 4 concentrations of TCE (approximately

300, 600, 1000, and 1300 mg/nr), each at 5 levels of relative humidity (5,

25, 50, 65, and 85%). Temperature levels were maintained at 23 ± 2 °C.

Determination of adsorption capacity was based on time to 50% TCE

breakthrough and the assumption of a symmetrical breakthrough curve. The

author concluded that relative humidity at 5 different levels affected the

adsorption capacity of activated carbon (for TCE); that, in general, each

increase of humidity level further decreased the carbon’s adsorptive

capacity at all 4 concentrations of TCE tested; that the effect of relative

humidity was greater at low TCE concentrations than at high TCE

concentrations; that the Dub in in- Pol any i adsorption isotherm equation fit

data at each humidity level equally well; and that the basis of the equation

might be useful for predicting the effect of humidity on gaseous phase carb- on adsorption.

[64] Willey, M. A., McCammon, C. S., and Doemeny, L. J.

A Solid Sorbent Personal Sampling Method for the Simultaneous

Collection of Nitrogen Dioxide and Nitric Oxide in Air

Am. Ind. Hyg. Assoc. J. 38, 358-363 (1977)

A solid sorbent sampling tube for nitrogen dioxide (NO^) and nitric oxide

(NO) and a sampling method for the collection of air samples containing both

NO^ and NO in the range 0.5 to 5 ppm NO^ and 9 to 50 ppm NO, are described

in this paper. The sorbent sampling tube consisted of a pyrex glass tube

containing two 400-mg sections of triethanolamine (TEA) -impregnated molecular

sieve and one 800-mg section of oxidizer. A single solid sorbent tube could

be used to sample in an occupational environment and collect NO^ and NO.

The NO,., was collected on the front section of TEA-impregnated molecular

sieve, the NO was converted to NO^ by the oxidizer and then passed into

another TEA-impregnated molecular sieve section where it was collected as NO^. The TEA sections were desorbed separately and analyzed by a spectrophotometer. At all concentrations tested, the collection efficiency

for N0

? averaged approximately 96%. The collection efficiencies for NO

were: at 9 ppm, 97%; at 11 ppm, 106%; at 24 ppm, 84%; at 50 ppm, 67%.

26
B. STANDARD OPERATING PROCEDURES

[P1J Berkley, R. E. , Bumgarner, J. E., Driscoll, D. J., Morris, C. M., and

Wright, L. H.

Standard Operating Procedure for the GC/MS Determination of Volatile

Organic Compounds Collected on Tenax Environmental Monitoring Systems

Laboratory

U. S, Environmental Protection Agency, Research Triangle Institute,

N. C., Stanford Operating Procedure EMSL/RTP-S0P-EMD-02L, Revision 0,

June 27, 1984

This detailed standard operating procedure consists of thermal desorption of

trace organic containants in air collected on tenax-GC porous polymer,

separation of the collected compounds into fractions by high resolution

capillary column gas chromatography, and analysis by low resolution electron

impact mass spectrometry. A computer-assisted data reduction procedure,

used to identify and ’'quantitative" selected compounds, was written specifically for the Finnegan 4023 gas chromatograph/mass spectrometry/

computer system; it may not be directly applicable to other instruments.

[P2] Berkley, R. E., Swanson, D. H., and Bumgarner, J. E.

Standard Operating Procedure for the Preparation and Use of

Standard Organic Gas Mixtures in a Static Dilution Bottle

Environmental Monitoring Systems Laboratory,

U. S. Environmental Protection Agency, Research Triangle Park, N.C.

Standard Operating Procedure EMSL/RTP-SOP-EMD-001 , Revision 1,

July, 1982

In this procedure, standard organic gas mixtures are prepared by injection

of a quantity of liquid organic compound through a septum cap into a heliumfilled flask. A large number of different compounds may be injected, flasks

with as many as 34 compounds had been used successfully. The flask is

agitated and heated to achieve complete vaporization, after which aliquots

of the vapor are delivered to sorbent cartridges or analytical instruments.

[P3] Berkley, R. E.

Standard Operating Procedure for the Preparation of Tenax Cartridges

Containing Known Quantities of Organics Using Flask Vaporization

Environmental Monitoring Systems Laboratory,

U. S. Environmental Protection Agency, Research Triangle Park, N.C.

Standard Operating Procedures EMSL/RTP-SOP-EMD-01 2

,

Revision 0, November, 1981

In this procedure, a dilute solution of one or more organic compounds in

methanol is heated in a heated zone (310 + 10 °C) in a helium stream. The

rapidly vaporized methanol and solute compounds are swept into a sorbent

cartridge. Methanol has little affinity for Tenax-GC and is rapidly eluted

from the cartridge. The solute compounds may be subsequently desorbed from

the cartridge and delivered to an analytical instrument. The method may be

used to spike quantitative standards on sorbent cartridges.

[P4] Bumgarner, J. E.

Standard Operating Procedure for the Preparation of Clean Tenax

Cartridges

Environmental Monitoring Systems Laboratory,

27
U. S. Environmental Protection Agency, Research Triangle Park, N.C.

Standard Operating Procedure EMSL/RTP-S0P-EMD-01 3,

Revision 0, November, 1981

This procedure covers the preparation of a batch of twenty Tenax-filled

cartridges for sampling ambient air. The Tenax is cleaned in a Soxhlet apparatus using methanol and pentane as solvents. The Tenax is then dried by

successively heating in air and in a vacuum oven, sieved into a breaker, and

added through a powder funnel into a glass cartridge. The cartride is

tapped gently to settle approximately 1 .5 grams of Tenax. The packed

cartridges are then conditioned (twenty at a time) at 270 °C under a helium

purge.

[P5] Walling, J. F. and Bond, A. E.

Standard Operating Procedures for Sampling Gaseous Organic Air

Pollutants for Quantitative Analysis Using Solid Absorbents

Environmental Monitoring Systems Laboratory,

U. S. Environmental Protection Agency, Research Triangle Park, N.C.

Standard Operating Procedure EMSL/RTP-SOP-EMD-018, Revision 1,

January, 1984.

This procedure provides instructions which permit defensible interpretations

of analytical data for ambient air sampling for organic molecules. The sam- pling consists of drawing air through a cylindrical cartridge packed with a solid adsorbent. The preferentially adsorbed organic species are subsequently thermally desorbed into a gas chromatograph with mass spectrometric detection.

[P6] Blau, P. A.

Standard Operating Procedure for the Storage of Samples at the Field

Sampling Site

Research Triangle Institute (Research Triangle Park, N.C.)

Standard Operating Procedure RTI/ACS-SOP-431 -001 (Air), SOP-432-001

(Water), SOP-437-001 (Breath), Revision 1, April, 1984

This standard operating procedure gives the details of the routine for storing and preserving samples at the field sampling site, including methods for

handling both Tenax (breath, air, and fixed site) and water samples. The

procedure is applicable to any sampling trip/field site. Tenax samples re- quire isolation and controlled atmosphere storage, water samples require

refrigeration.

[P7] Brady, K. A.

Standard Operating Procedure for the Quantitation of Volatile Organic

Compounds in Air and Breath Tenax Samples

Research Triangle Institute (Research Triangle Park, N.C.)

Standard Operating Procedure RTI/ACS-SOP-71 1 -001 (Air), SOP-717-001

(Breath), Revision 0, January, 1984

This standard operating procedure describes the method used to ’’quantitate"

the target compounds in air and breath Tenax samples that had been analyzed

by gas chromotograph/mass spectrometer (GC/MS). Two BASIC computer programs

were written to facilitate the quantitation. After each Tenax sample

cartridge is analyzed, a data report listing the ion intensities or mass for

each target compound is prepared; similar reports are prepared for the

28
blanks and controls from each Tenax batch. The relative molar response of

the instrument for each target compound is determined from analysis

of cartridges loaded with known amounts of the targets, and the limits of

detection for each instrument for the target compounds are determined. The

concentrations of the targets present in the samples are determined using

all this information.

[P8] Castillo, N. P.

Standard Operating Procedure for Preparing Response Factor Tenax

Cartridges Using a Permeation System

Research Triangle Institute (Research Triangle Park, N.C.)

Standard Operating Procedure RTI/ACS-S0P-630-005 , Revision 0,

May, 1984

This standard operating procedure describes the methodology for loading

Tenax cartridges using a dynamic dilution (permeation) system. The permeation system consists of three parts: 1) a temperature-controlled chamber

containing permeaton tubes; 2) a mixing chamber; 3) two cartridge holders

enclosed in an insulated jacket. The loaded cartridges are used to determine the response factor of the gas chromotograph/mass spectrometer/

computer system. The procedure consists of the following steps: 1) selection of the permeation tubes; 2) determination of the loading conditions

(flow rates and duration); 3) equilibration of the system; 4) checking of

the background of the Tenax cartridges; 5) loading of the cartridges; 6)

calculation of the amounts of compounds loaded; 7) assuring the integrity of

the loading procedure; 8) adding the external standards.

[P9] Castillo, N. P.

Standard Operating Procedure for Preparing Response Factor and

Column Performance Evaluation Tenax Cartrides Using a Flash

Evaporation System

Research Triangle Institute (Research Triangle Park, N.C.)

Standard Operating Procedure RTI/ACS-S0P-630-006 , Revision 0,

May, 1984.

This standard operating procedure is essentially the same as [PI 4]; in the

present case, the cartridges are to be used to determine response factor

rather than relative molar response.

[P10] Castillo, N. P. Standard Operating Procedure for Preparing Quality Control Samples on Tenax Cartridges

Research Triangle Institute (Research Triangle Park, N.C.)

Standard Operating Procedure RTI/ACS-S0P-860-001 , Revision 1

,

May, 1984

This standard operating procedure describes: 1) the steps to be followed to

select and label quality control samples; 2) the loading of Tenax control

cartridges with volatile organic compounds using a flask evaporation system;

3) the methodology for loading volatile organic compounds onto Tenax control

cartridges from a permeation system. The two types of control samples are:

1) spiked cartridges ("controls") used to determine recoveries of target

compounds after sampling; 2) unspiked cartridges ("blanks") used to determine the background of the Tenax cartridges and contamination associated

with sample transport and storage.

29
[P1 1 ] Castillo, N. P,

Standard Operating Procedures for Preparing Relative Molar Response

Tenax Cartridges Using a Permeation System

Research Triangle Institute (Research Triangle Park, N.C.)

Standard Operating Procedure RTI/ACS-SOP-630-001 , Revision 0,

January, 1984.

This standard operating procedure is essentially the same at [P8] ; in the

present case, the cartridges are to be used to determine the relative molar

response of the gas chromotograph/mass spectometer/computer system.

[PI 2] Castillo, N. P. Standard Operating Procedure for Loading Deuterated Standards on Tenax Cartridges Using a Permeation System

Research Triangle Institute (Research Triangle Park, N.C.)

Standard Operating Procedure RTI/ACS-SOP-630-004, Revision 0,

December, 1983.

This standard operating procedure describes the methodology for loading

Tenax cartridges with deuterated standards using a permeation system. The

loaded cartridges are subsequently used for sampling which allows for an as sessment of premature breakthrough. The system may be used to load any

volatile compound that will permeate at a constant rate under controlled

conditions, and may be used to inject a calibration standard onto a sorbent

using a syringe.

[PI 3] Castillo, N. P.

Standard of Operating Procedure for Loading External Standards on Tenax Cartridges Via Injection Using a Permeation System

Research Triangle Institute (Research Triangle Park, N.C.)

Standard Operating Procedure RTI/ACS-S0P-630-003, Revision 0,

December, 1983

This standard operating procedure describes the methodology for loading the

external standards, perfluorobenzene (PFB) and perfluorotoluene (PFT) onto

Tenax cartridges, by syringe injection from a permeation system. PFB is

used an an external standard to determine relative retention times and rela

tive response factors of the compounds to be "quantitated", PFT is used for

determining instrument stability as related to mass resolution and relative

ion abundance under gas chromatographic conditions.

[PI 4] Castillo, N. P. Standard Operating Procedure for Preparing Relative Molar Response

and Column Performance Evaluation Tenax Cartridges Using a Flash

Evaporation System

Research Triangle Institute (Research Triangle Park, N.C.)

Standard Operating Procedure RTI/ACS-SOP-630-002, Revision 0,

December, 1983

The purposes of this standard operating procedure are: 1) to describe the

methodology for preparing column performances evaluation (CPMX) solutions

and relative molar response (RMR) solutions; 2) to describe the loading of

Tenax-GC cartridges with volatile organic compounds and the CPMX components

using a flash evaporation system. The method is applicable to organic com- pounds the breakthrough volumes (defined as the volume of gas required to

30
elate 50% of a compound introduced into one end of a cartridge) of which are significantly greater than the volume of the diluting solvent. Also, the

retention of the solvent by the Tenax-GC must be minimal. The main body of

the flask evaporation system consists of a glass tube with an injection

port, the tube is maintained at 250 °C with heating tape. Any solution injected into the port is transported to a sorbent cartridge on line by a stream of helium gas. The CPMX solution is used to determine mass calibration of a gas chromatograph/mass spectrometer/computer (GC/MS/COMP) system.

The RMR solution is used to determine the relative molar response of the

GC/MS/COMP system.

[PI 5] Castillo, N. P.

Standard Operating Procedure for the Storage of Air Breath Tenax

Samples at Research Triangle Institute

Research Triangle Institute (Research Triangle Park, N.C.)

Standard Operating Procedure RTI/ACS-SOP-481 -001 (Air), SOP-487-001

(Breath), Revision 0, December, 1983

This standard operating procedure describes the proper manner of storing

Tenax cartridges on which air and breath volatiles were collected, prior to

analysis by a gas chromatrograph/mass spectrometer/computer system. A

freezer reserved for Tenax cartridges was deemed to be essential since

several studies had concluded that contamination of Tenax, both from external sources and from internal impurities, could be minimized by storing the

cartridge at -20 °C.

[PI 6] Castillo, N. F.

Standard Operating Procedure for Tenax Cleanup and Preparation of

Tenax

Cartridges for Use in The Collection of Organic Compounds

Research Triangle Institute (Research Triangle Park, N.C.)

Standard Operating Procedure RTI/ACS-SOP- 320-001 , Revision 0,

December, 1983

The two-fold purpose of this standard operating procedure was to: 1)

describe the methodology for cleaning Tenax; 2) describe step by step the

preparation and purification of the Tenax cartridges. The routine to be

followed consists of selection, solvent extraction, drying and sieving of

the Tenax; packing of the Tenax into glass cartridges; thermally desorbing

the cartridges; ensuring the integrity of the cleaning and desorbing procedures; and packing and storage of the cartridges.

[PI 7] Porch, R. L. Standard Operating Procedure for the Analysis of Volatile Organics

Collected on Tenax Using the Finnigan 3300 GC/MS/DS

Research Triangle Institute (Research Triangle Park, N.C.)

Standard Operating Procedure RTI/ACS-S0P-533_ 002, Revision 0,

April, 1984

This procedure, applicable to the qualitative and quantitative analysis of

volatile organic compounds collected on Tenax GC, is related to optimal procedures for a particular instrument although the author claims that the

basic method is adaptable to any gas chromatograph/mass spectrometer/data

system (GC/MS/DS) with a suitable thermal desorption unit. Organic vapors

collected on Tenax-GC is thermally desorbed, cryofocussed, and analyzed

31
using the GC/MS/DS. The method is limited by the adsorption of water on the

Tenax-GC since excess water will freeze the cryofocussing trap making quantitative analysis impossible.

32
SUBJECT INDEX

absorbing solution

accuracy

acetic acid

acetone

acetonitrile

acid aldehydes

acid halides

acid vapor

acrolein

acrylonitrile

activated carbon

adsorbent

adsorbent, porous polymer

activated charcoal

adsorbent beds, tandem

adsorbent tube

adsorbent tube, reagent-coated

adsorption

adsorption, volatile phase

adsorption, water

adsorption capacity

adsorption isotherm

adsorption of water

adsorption solvent

adsorption tube sampling system

air currents

air gap

airflow rate

air quality

alcohol

Amberlite

Ambersorb

amines

amyl alcohol

analysis of variance

analytical data

Anasorb

anhydrides

anhydrides, acetic

Arcolor

area sample

aromatic

aromatic diamine

aromatic polyimide resin

automated analysis

automated sequential syringe sampler

33

10, 17, 25, 36, 39

40, 65

7, 24, 41 7

38

38

65

28

8, 9, 11, 41

28, 29, 59, 63, 67, 68

1, 12, 13, 16, 22, 28, 30,

31, 43, 53, 56, 59, 60-62,

65-67

11 , PI 22, 24, 41, 56, 59, 65-67

60, 61 13, 31, 37

3

1, 12, 24, 29, 53, 56, 62

63, 65-68, P5

63

PI 7

63, 65

56, 63

PI 7

4111, 31

52

11

159

38

20, 23

413, 23, 38

24

26, 55

P5

20

38

38

13

26

48

18

18

12

32

33
automatic two-channel air sampler 48

automation 32, 36, 42

automation, laboratory 36

background 25, 26, P8, P10

badge 20, 33, 34, 59

badge, formaldehyde 17

badge, organic vapor 25, 33, 34

badge-type diffusion sampler 12, 59

bag sample 6

benz[a]-anthracene 44

benzene 11, 12, 25, 39, 55

benzophenonetetracarboxylic acid 18

blank 15, 37, 59-61, P7, P10

body burden 59

breakthrough 24, 54, 63, 66, P12

breakthrough curve 63, 65, 66

breakthrough time 1, 22, 29, 67

breakthrough volume 8, 13, 22, 53, PI

breath level 58

breath sample P6, P7, PI 5

breathing-zone air 59, 68

bromine 15

butadiene, 1, 3" 17

butene, 2- 15

butoxyethyl phosphonate, bis 20

butyl acrylate, N- 52

calibration 10, 14- 16, 28, 39

calibration curve 10, 28, 43

calibration factor 10

calibration standard 28, PI 2

canister 1 capacity 5, 25, 61, 66

capsule, sorbent 42

carbon, activated 28, 29, 56, 59, 63, 66-

carbon, graph itized 47

carbon dioxide 44

carbon disulfide 24, 41, 55, 59

carbon sorbent 15, 47

Carbopack 15

Carbosieve 8, 41

Carbowax 15, 28, 57

cartridge 1, 15, 37, 43-48, 51, 1 60, 62, 66, 67, P2-P17

cartridge, respirator 66, 67

centrifuge tube 30

charcoal 17, 22, 24, 35, 48, 52

56

charcoal, activated 22, 24, 41

charcoal, coconut-based 24

charcoal, impregnated 17, 30

charcoal cloth 4

charcoal tube 17, 19, 35, 36, 52, 54

34
charcoal tube/solvent desorption, pumped

Chemical Defense Establishment

Chemical Research and Development Center

chemical transformation

chemisorption

chlorinated hydrocarbon solvent vapor

chloroacetly chloride

chloroethyl ethyl sulfide

chloride

chlorine

chloroform

chlorotrifluoroethylene

chromatograph column vibrator

chromatographic theory

chromatography

Chromosorb

cleaning of Tenax-GC

collection, simultaneous

collection efficiency

collection of samples

colorimeter

colorimetric analysis

column performance

computer-assisted data reduction

concentration, vapor

concentration gradient

concentration level

concentration profiles

conductimetric detector

contaminant

contaminant concentration

contamination

control

cresol

cryofocussing

cryogenic trap

cyclohexane-d^

cyclohexene

54

4, 20

20

45

1, 3

54

38

20

40

15

27, 29

19

22

53, 62

3, 15, 36, 57

1, 2, 5, 14, 24, 27, 28, 47,

65

P4

64

22, 49, 53, 64

20, 48, 57, 60, 65, 67, PI

5

33, 34

P9, PI 4

PI13, 14, 17, 50, 60

12

25, 26, 54, P7

39

30

1, 13, 15, 22, 26, 37, 51,

56, 60, 62, 66, 67, PI , P10,

PI 5

67

51

26, 57, 58, P7, P10

68

37, 58, 60, PI

48

45

15

data interpretation

decomposition of chemical substances

decomposition products

degradation

derivatization

desiccant

desorption

62

15

46

3, 46

3, 23, 28, 38

5, 6

2, 5, 7, 14, 19, 22, 24, 25,

27, 28, 36, 37, 41, 42, 44,

45, 54, 55, 57, 61, 64, 65,

PI , P5, PI 6, PI

36

7, 28

desorption, whole- tube

desorption efficiency

35
desorption solvent 14, 28

detection, limit of 57, 60

detector, nitrogen-selective 41 deuterated compounds 45, 60

deuterated standard P2, P12

dew-point hygrometer 49

diamine, aromatic 18

diatomaceous earth 65

dichloroacetic acid 40

dichlorodiethyl ether, 2,2’- 2

diethylamine 23

diethylether 68

diffuser element, multi-cavity 17

diffusion 10, 33, 55, 56

diffusion, molecular 6

diffusion monitor, passive 6

diffusion sampler, badge-type 12, 59

diffusional resistance 14 diffusive sampler 10, 11, 16, 20, 49

diffusive sampling 49

diffusive uptake 16

di isopropyl methylphosphonate 20

dilution 43

dimethyl amine 23

dimethyldichlorosilane 27

dinitrotoluene 27

displacement 24

distilled deionized water 17, 40

distilled water deorption 65

distributed air volume sets 60, 61

dosimeter 25, 39, 42, 52

dosimeter, passive 25, 39, 42, 50

dosimeter system, multisorbent passive 42

dosimetry 4

drying agent 5

dual-bed collection tube 8

Dubinin-Polanyi adsorption isotherm 63

Dubinin-Radeshkevich adsorption isotherm 56

Duncan’s multiple range test 26

dynamic atmosphere generation 9, 41

dynamic dilution system P8. P9, P11

dynamic sample 4

dynamic vapor pressure system 35, 39

efficiency 25, 26

electrochemical fuel cell 17

electron capture detector 7, 15, 36, 54, 59,

electron impact mass spectrometry PI emission, source 26

environment 33, 64, 65

environmental sampling 50

ethanol 24

ethene 44

ethyl acrylate 52

36
ethylamine

ethylene

ethylene chloride

ethylene oxide

ethylenediamine

evaluation, field

exhaled air

explosive

exposure

exposure, time-weighted

exposure, time-weighted average

exposure agent

exposure concentration

exposure limit, short-term

exposure period

exposure time

external air movement

external flow effects

external mass-transfer resistance

external standard

23

15

28

33, 3*1 3

6, 10, 11, 15, 55

59

7

16 , 16

17,

6

10 , 17,

16

10 , 10

1149

36,

26, 39, 58, 59

19, 35

35

25

12

38, P8, P9, P11

face velocity

field comparison

field evaluation

field sampling

field spiking

field testing

field validation

field verification

filter, glass fiber

filter, reactive

filter, Teflon

filtration

fixed bed

fixed site sample

flame ionization detector

flame photometer detector

flash vaporization

Florisil

flow system, two-phase

flowrate

flowrate, kinetic saturation

fluorescence detector

fluoride

fluorimeter

food

f ormaldehyde

formaldehyde badge

formaldemeter

formate

formation of chemical substances

formic acid

12, 15, 25

6

6, 11, 15, 55

35, 46, 47, 62, P6

9

10, 11, 17, 19

8, 9

9, 33, 34

15

40

46

30, 45, 46

62

P6

2, 15, 19, 22, 24,

35, 36, 39, 41, 54,

21

P3, P9, P10, PI

7, 14

62

13, 22, 24, 39, 44,

67, P8, P9, P11

22

23

40

5, 17

59

5, 17, 30, 34

17

17, 34

30

15

65

, PI 3

28, 29,

55, 62

60, 62,

37
free fatty acid phase

f reezer

2, 24, 27

PI 5

gas adsorption kinetics

gas badge

Gas Chrom

gas chromatography

gas chromatography/mass spectrometry

gas chromatography/mass spectrometry/

computer system

gas liquid chromatography

gas-tight syringe

generation, vapor

glycolic acid

grab sampler

graphitized carbon

gravimetry

66, 67

52

7, 21, 29

2, 7, 8, 11, 13, 15, 18-20,

22 24, 25, 27-29, 35-37, 39-

41, 43, 44, 48, 54, 55, 59,

61-63, 68, PI, P5, PI

43, 45, 46, 59, 60, 61, PI,

P5, P7-P9, P11

15, 37, 58, PI, P8-P11, PI 4,

PI 5 , pi 7

15

43

7

40

31

47

11

halogenation

hazardous vapor

hazards

heat transfer

hexane

high-performance liquid chromatography

high-performance thin layer chromatography

high-pressure liquid chromatography

humidity

hydraquinone

hydrazine

hydrazoic aid

hydrocarbon

hydrocarbon, aromatic

hydrocarbon, halogenated

hydrocarbon, trichlorinated

hydrochloric acid

hydrofuran

hydrophobic ity

45

37, 47, 50

50

114, 22, 38

3, 23, 57

38

57

4, 8, 10-14, 16, 21, 23, 25,

29, 34, 35, 38, 40, 41, 63

28

17

65

48, 56, 60

44, 48, 60, 61

15, 48, 60, 61

66

65

3

7

impinger

impinger method, xylene

impinger/polarographic system

impregnated charcoal

impregnated charcoal tube

in situ measurement

in situ reaction

indoor-outdoor relationships

industrial hygiene

inertness

65

21

17

30

17

3145

58

9, 26, 35, 36, 50, 55, 66,

67

7

38
infrared analyzer 6, 52

inhibition 45

inorganic gas 46, 48

inorganic gas, reactive 46

interactions 56

interference 5, 10, 17, 21, 38, 48,

internal mass transfer resistance 49

ion chromatography 30, 40

ion-exchange chromatography 30

isocyanate 38

isocyanatoethyl methacrylate 38

isopropanol 24

iso-octane 39

kinetic adsorption 29

kinetic saturation capacity 22

laboratory automation 36

laboratory experiment 10, 11, 15, 18, 19, 62

laboratory robot 36

laboratory test 17, 42, 48

laboratory validation 19, 33, 34, 35, 41 leaching 68

least significant difference test 55

limit of detection 41, 57, P7

loading of cartridge P8, P10

loading of deute rated standard PI 2

loading of external standard PI 3

low-volatility compounds 2

mass spectrometry

mass spectrometry, low resolution electron

PI

impact PI mechanical shaker 23, 38

methane 44

methanol 14, 15, 24, 57, P3, P4

methyl acetate 66

methyl benzilate 20

methyl salicylate 2

methylamine 23

microcomputer-controlled syringe 31

miniature passive dosimeter 25

Mini monitor 20

minimum detectable quantity 3

moisture 29

molar response, relative P7, P11 , PI 4

molecular diffusion 6

molecular sieve 6, 16, 49, 64

monitor, passive diffusion 6

monitoring 9, 11 , 17, 25, 31, 34,

38, 41 6

20

33, 34

monitoring, real-time

monitoring badge, organic vapor

monitoring badge, passive air

39
monochloroacetic acid 40

multicavity diffuser element 17

multicomponent volatile organic standard 43

multiple comparisons 10

multisorbent passive dosimeter 42

N-butyl acrylate 52

National Bureau of Standards 39

NBD chloride 23

nitric oxide 64

nitrogen 13, 15

nitrogen dioxide 49, 64

nitrogen-selective detector 41

nitrosation 45

nitrous oxide 6, 16

non-polar organic vapors 24

organic analysis, vapor phase 18

organic chemical, gaseous 62

organic compounds 46, 58, 60, PI, P3, P5, PI

organic compounds, volatile 17, 37, 59, 62, 63, P7, P10,

PI 4, PI 7

organic gases 46, P5

organic pollutants 48, P5

organic solvent concentration 52

organic vapor 2, 12, 13, 20, 24, 25, 37,

45-47, 51, 54, 55, 58

organic vapor monitoring badge 20, 25

oxidant 17, 46

oxidation 3, 45

oxidizer 64 ozone 46

ozonization 45

packing 14, 65, P4, PI

passive air monitoring badge 33, 34

passive diffusion monitor 6

passive dosimeter 25, 39, 42, 52

passive dosimeter system, multisorbent 42

passive sampling 4, 57

passive organic vapor sampler 55

passive sampler 4, 31, 55, 56

pentachlorophenols 68

pentane 15, P4

perfluorobenzene PI 3

perfluorotoluene PI 3

permeable membrane badge 59

permeation 10

permeation system P8-P13

permeation tube 62, P8, P9 P11

phenol 68

phosphine 21 phosphorus, red 21

phosphorus, white 21

40
phoroionization detector 39

piperazine 38

polar organic vapors 24

polarographic reduction 7

pollutant 12, 13, 25, 3

58, 59, 62, P polycyclic aromatic hydrocarbon 44

polyimide resin, aromatic 18

polymer, porous 21

polymellitic dianhydride 18

polynuclear aromatic hydrocarbon 44

polymeric beads 37

polymerization inhibitor 28

polypropylene 4

Porapak 11, 12, 19, 2 precision 8, 10, 16, 21

43

preconditioning, thermal 15

prediction 63, 66, 67

pressure 10, 21, 34, 5 pressure drop 65

propane 44

propoxur 57

propylene 15

protocol 10

pump, personal sampling 19, 21 , 24

pump/charcoal tube sampling method 33

pump/impinger sampling method 34

pump method, conventional 16

quality assurance 48

quality assurance standards 43

quality control 48, P10

quantitative analysis P5

quantitative standards P3

quartz fiber, impregnated 40

RDX vapors 7

reaction 5, 15, 60, 61

reaction, chemical 60, 61

reaction, halogenation 45

reaction, nitrosonation 45

reaction, ozonization 45

reaction products, apparent 60, 61

reactive chemicals 38

reactive chemicals, airborne 38

reactive filter 40

reactive gases 15

reactive inorganic gases 46

reagent 33, 38

recovery 8, 9, 14, 30,

recovery, sample 4, 65 , 68

relative molar response P7, P11 , Pi 4

relative response factor Pi 3

41
reliability

resolution

residence time

respirator

response factor

retention

retention time

retention time, relative

retention volume

reversibility

robotics

36

44

1

1P8, P9

56, 57, 60, 62, PI

28

PI 3

13, 18, 53, 62

56

36

safe sampling volume

sample

sample recovery

sample tube

sample, air

sample, area

sample, breath

sample, fixed site

sample, gaseous atmospheric

sample, replicate

sample, transfer of

sample, transportation and storage

sample, water

sampler

sampler performance

sampler, adsorbent

sampler, air, automatic, two-channel

sampler, grab

sampler, liquid, automatic

sampler, personal

sampler, syringe, automated sequential

sampler, tube-form

sampling

sampling and analysis

sampling efficiency

sampling pump

sampling time

sampling system, adsorption tube

sampling tube

sampling, air

sampling, field

sampling, personal

sensitivity

sequential grab sampler

sequential monitoring

sequential syringe sampler

service life

13

23,

4

8

P6,

26

P6,

p6

49

15

48

25

P6

16 , 55,

10 , 53

48

3135

31,

25,

P7,

P7,

20 , 58

47,

58

P6, P10

PI 5

PI 7

32, 35, 47, 49, 53,

55

32

11 , 12

5 , 9 , 10 , 16 , 18 - 20 , 21 , 23 , 24, 26-28, 30, 31, 33, 35-

37, 40-42, 45-51, 53-58, 60-

62, 64, 65, 68, P4, P5, PI

54

56

21

31

11, 31

5, 21, 27, 30, 61, 65

26, 33, 45, 50, 60, P5

35, 46, 47, 62, P6

5, 10, 11 , 16, 19, 21 , 24,

28, 64, 68

17, 25, 28, 68

3125

32

66, 67

42
shaker, mechanical

short-term exposure limit (STEL)

silica gel

simulated sampling

simultaneous collection

sodium bicarbonate

sodium bisulfite

sodium carbonate

sodium hydroxide solution

sodium thiosulfate

solid adsorbent

solid sorbent

solid sorbent sampling tube

solvent

solvent desorption

solvent extraction

solvent vapor hazard

sorbent

sorbent background

sorbent bed

sorbent, carbon

source sampling

Soxhlet extraction

spectrophotometer

spike

stability

standard

standard, calibration

standard, deuterated

standard, external

standard, multicomponent volatile organic

standard, primary

standard, quality assurance

standard, quantitative

standard, volatile organic

standard atmosphere

standard curve standard deviation, relative

standard operating procedure

standard organic gas mixture

static dilution, bottle

static sampling

statistical method

statistical tests

storage

storage, loss on storage and shipping conditions, sample

storage media

23, 30, 38

17, 25

19, 24, 27, 40, 49

62

64

23, 40

17

65

68

15, 45, 46

7, 23, 38, 62, P5

5, 7, 8, 13, 20, 21, 23, 28,

30, 38, 40, 42, 43, 61 , 64,

65, P5

21, 23

14, 28, 41, 50, 54, P4

41, 42, 54, 55, 57, 59

21 , PI 6

50

1, I 1*, 15, 18, 19, 22, 23,

25, 36, 38, 40-42, 45-49,

51, 57, 64-67, P2, P3, P4,

P12 , PI 4

18

115, 47

3115, P4

64

7, 9, 14, 16, 18, 36, 45,

60, P3, P10

5, 25

3, 36, 39, 43

28

PI 2

36, 38, P8, P9, P1 1 , PI

43

39

43

P3

23, 43, PI 10

28

30

PI —PI 7

P2

43, P2

10 , 11 9

26

8, 25, 40, P6, P15, PI

54

2148

43
storage stability

storage of Tenax cartridges

styrene

styrene-dg

sulfur dioxide

sulfuric acid

Supelcoport

4, 38, 40, P6, P10

PI 5, PI 6

11, 52

45

49

5, 49

57

tandem beds

Tedlar

temperature

Tenax-GC

Tenax-GC, cleaning of

test apparatus

test mixture

tetrachloroethene

tetrachlorome thane

tetrachlorophenols

tetrahydrafuran

thermal desorbability

thermal desorption

thermal desorption, total injection

thermal stability

thermogravi metric analysis

theoretical plates

threshold limit value

time-weighted average exposure (TWA)

time-weighted exposure (TWE)

TNT vapors

total injection thermal desorption

toluene

toxic organic pollutants

trace analysis

trace level organic analysis

trace organic vapor pollutant

tracer studies, atmospheric

transfer pipe

transformations, chemical

transport

trap

trichloroacetic acid

tri chloroethane , 1,1,1-

trichloroethene

trichloroethylene

tricloromethane

triethanolamine

trimethylsilyl derivative

tube

tube, adsorbent

tube, adsorption, sampling system

60 , 19

4,

7,

48,

P6-

P1

10

39

54

54

68

3,

44

2 , 39,

P5,

8

47

18

53

27

17,

16

7

8

19,

31,

3

18

47

32

2

45

9,

37,

40

54

54

63

54

64

68

38

13,

11 ,

61

10, 11, 13, 21, 40, 44

8, 11-15, 18-21, 37, 44-

51, 58-62, PI, P3, P4,

PI 7

23

6, 8, 1 1, 13, 15, 25, 37,

42, 44-46, 58-61, PI,

PI 6, PI 7

19, 35

24, 55, 66

48, 58, 59

25, P10

48, 59

23, 31 31

44
tube, charcoal 35, 36, 52, 54

tube, charcoal, impregnated 17

tube, sorbent 14, 22, 40, 57

tube-type diffusive sampler 12

turbulence 12

two-phase flow 62

ultra-sonic bath 30

ultraviolet absorptivity 3

ultra-violet/visible detector 23

uptake, diffusive 1

uptake rate 10

uptake rate, standard 10

U.S. Air Force 6

validation 8, 34, 40, 41

validation, field 9

validation, laboratory 33-35, 41

valve, gas sampling 8

verification, field 33, 34

vapor exposure system, dynamic 39

vapor hazard ratio 50

vapor hazard index 50

vapor pressure 12, 50

vibrator, chromatograph column 22

vinyl chloride 59, 66

volatile compound PI 2

volatility 2

vortexing 14

water, distilled deionized 40

water, low retentive index for 47

water vapor 5, 13, 21, 29,

water vapor, affinity for 13

whole tube desorption 36

XAD-2 3, 12, 14, 15

xylene 21, 24, 55

45

40, 49
AUTHOR INDEX

Ackley, M.W. 1 Alder, J.F. 2

Anderson, K. 3

Ansul, G.R. 33, 34,

Ayers, T.A. 7

Bailey, A. 4 Baldwin, C.L. 17

Barrett, W.J. 21

Basilio, A.N. , Jr. 33, 34

Benner, R. 32

Berkely, R.E. 43, 47,

Bisgaard, P. 5

Bishop, E.C. 6

Bishop, R.W. 7

Blau, P.A. P6

Bond, A.E. P5

Borders, R.A. 8, 9, 41 Bouyoucos, S. 17

Brady, K.A. P7

Brown, R.H. 10, 11,

Brownlow, C.S. 14

Bryant, M.L. 20

Bumgarner, J. 43, 60,

Bunch, J.E. 15, 47

Campbell, R.A. 36

Castillo, N.P. P8-P16

Charlton, J. 1

Cook , R.E. 17

Cooper, S. 48

Coyne, L.B. 17, 36,

Cox , P c C16

Crouse, W.E. 26

Damrell, D.J. 33

Demain, B. 18, 46

Demaray , D . E

31, 32

Dietz, E.A., Jr. 19

Dillon, H.K. 20, 21

Dixon, S.W. 35

Doemeny, L.J. 64

Douglas, J.J. 33

Driscoll, D.J. 60, PI

Easley, L.D. 22

Eller, P.R. 21 Elskamp, C.J. 23

Erickson, M.D. 59

Esposito, G.G. 65

45

62, PI , P2 , P3

12, 13, 16

PI , P2 , P4

41

46
Falbo, L. 52

Farris, T.S. 29

Fowler, W.F. 20

Geraci, C.L. Jr. 30

Glaser, R.A. 40

Gluck, S.J. 8, 9

Goller, G.W. 24

Gonzalez, J. 25, 39

Gutknecht, W.F. 48

Hallgren, C. 3

Hardison, D. 48

Hartwell, T.D. 58, 59

Harvey , R . P

10

Heitbrink, W.A. 26

Hemingway, R.E. 35

Henry, T.T. 33, 35

Hildebrand, E.A. 2

Hodgson, A.T. 49

Hoffman, V.J. 19

Hollingdale-Smith, P.A. 4

Hossain, M.A. 6

Hubbard, S.A. 37

Hunt , R . J

27

Hurley, G.F. 28

Jonas, L.A. 29

Kastl, P.E. 36

Ketcham, N.H. 28

Killough, P.M. 51

Kim, W.S. 30

Krasnec, J.P. 31, 32

Kring, E.V. 33, 34, 35, 39

Kristensen, T.J. 44

Kropscrott, B.E. 36

Krost, K.J. 37, 45, 46

Kupel, R.E. 30

Kvartek, E.J. 57

Lam, L. 18

Lamb , B32

Langhorst, M.L. 38

Lefebre, H. 42

Levin, J.-O. 3

Levine, S.P. 25, 39

Martin, J.J. 20

Mason, D.W. 40

McCammon , C . S . , Jr. 64

McDonald, O.F. 17

McGibney, P.D. 33, 34

McRae, J. 47

Melcher, R.G. 8, 9, 41

47
Molhave, L.

Moore, G.

Morello, J.A.

Morris, C.M.

5

42

35

43, 60, PI

Nann, J.R.

Nelson, J.H.

Neubauer, N.R.

Nilsson, C.-A.

17

66, 67

27

3

O’Dell, H.L. 34

Pankow, J.E.

Pellizzari, E.D.

Persoff, P. Picone, R.F.

Popendorf, W.

Porch, R.L.

Purnell, C.J.

44

15, 18, 37, 45, 46, 47, 48, 58, 59

49

27

50

PI 7

10, 13

Que Hee, S.S. 14

Reinhart, D.S.

Reitz, A.E.

Riley, A.E.

Rosenzweig, M.

Russwurm, G.M.

7, 65

5

60

59

51

Samimi, B.

Sansone, E.B.

Sarver, E.W.

Saunders, K.J.

Schindler, A.

Schultz, G.R.

Senum, G.I.

Sheldon. L.S.

Sowle, W.F.

Sparacino, C.M.

Spee, T.

Steinle, S.

Stephens, J.S.

Stikeleather, J.A.

Stockton, S.D.

Suggs, H.J.

Swanson , D . H

Sykes, J.A.W.

52

29

20

10, 11 18

23

53

58

8, 36

58, 59

54

42

34

51

55

22

62, P2

2

Toth, F.J. 62

Underhill, D.W. 55, 56

Vasta, J.F. 35, 57

Walburn, S.G.

Walkin, K.T.

37

12

48
Wallace, L.A. 58, 59

Walling, J.F. 60, 61

Werner, M.D. 63

Wilhardt, P. 5

Willey, M.A. 6A

Williams, K.E. 65

Windsor, J.G., Jr. 51

Wright, L.H. 60

,

PI

Yoon, Y.H. 66, 67

Yrjanheikki, E. 68

Zelon, H. vOl GO 59

49
NBS-114A (REV. 2*90

U.S. DEPT. OF COMM. 1. PUBLICATION OR 2. Performing Organ. Report No. 3. Publication Date BIBLIOGRAPHIC DATA

REPORT NO.

SHEET (See Instructions) NBSIR 87-3527 February 1987

4. TITLE AND SUBTITLE

Collection and Analysis of Organic Compounds in Air: An Annotated

Bibliography (1976-1986)

5. AUTHOR(S)

Frank E. Jones

6. PERFORMING ORGANIZATION (If joint or other than NBS. see instructions) 7 . Contract/Grant No. NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

8. Type of Report & Period Covered

9. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. State, ZIP)

Commander

Chemical Research Development and Engineering Center

SMCCR-RSP-P/Dr . Amnon Birenzvige

Aberdeen Proving Ground, MD 21010-5423

10. SUPPLEMENTARY NOTES

Q3] Document describes a computer program; SF-185, FIPS Software Summary, is attached.

11. 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 is a selected and annotated bibliography of sources of methodology for the

collection and analysis of volatile and semi—volatile organic compounds present

in air. The most prevalent methodology is the collection and preconcentration

of organic compounds in a tube or cartridge containing an adsorbent, and subsequent

thermal desorption of the collected compounds on the column of a gas chromatograph

(GC), GC/mass spectrometer (MS), or GC/MS/computer system for analysis. The

performance of adsorbents such as porous polymer adsorbents, and the optimization

and standardization of methodology are of particular interest., The bibliography

comprises 68 general citations and 17 standard operating procedures.

12. KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolon s) Adsorption; adsorbent cartridges; bibliography; analysis; GC/MS/computer systems;

porous polymer adsorbents; standardized methodology; thermal desorption; volatile

and semi-volatile organic compounds

13. AVAILABILITY

[X] Uni imited

[33] For Official Distribution. Do Not Release to NTIS

~

] Order From Superintendent of Documents, U.S. Government Printing Office, Washington, D.C.

20402.

[X] Order From National Technical Information Service (NTIS), Springfield, VA. 22161

14. NO. OF

PRINTED PAGES

57

15. Price

$13.95

U S COMM'DC 6043-P80
'