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Nafion Dryers

Nafion Dryers

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TN-85-03

NOVEMBER 198~

VALUATION

OF VARIOUS CONf.GURATIONS
.. ~--

OF NAFION DRYERS:
-"

WATER
{

~tEMOVAL

FROM AlfLSArv1PlES PRIOR TO GAS .

Subm;tf~dto:

Protection Agency Environmental Monitoring Systems Laboratory Research'Trianqle Park, NC 27711
•• • :. • I

u.s. Environmental

Under Contract 68-02-4035

TN-4120-85-03 NOVEMBER 1985

EVALUATION OF VARIOUS CONFIGURATIONS OF NAFION DRYERS: WATER REMOVAL FROM AIR SAMPLES PRIOR TO GAS CHROMATOGRAPHIC ANALYSIS

by

Joachim D. Pleil and Karen D. Oliver Chemistry and Field Monitoring Research Northrop Services, Inc. - Environmental Sciences Research Triangle Park, NC 27709

Submitted to:

W;Hiatft A. McClenny Methods Development Branch
EnV'rrortmentCft Monitor'ing Systems laboratory US. Environmental Protection Agency Research lriatlgi'e Park, NC 27711

Reviewed and Approved by.

,fL~t/~

N. E. Short Program Manager

P.o. Box 12313 Research Triangle Park, NC 27709

NORTHROP SERVICES, INC. ENVIRONMENTAL SCIENCES

Environmental Sciences

NORTHROP
DISCLArMER

TN-4120-8S-03

This report has been reviewed by Northrop Services, Inc. - Environmental Sciences and approved for publication. Mention of trade names or commercial products does not constitute endorsement or recommendation for use.

II

NORTHROP Environmental Sciences
FOREWORD

TN-4120-85-03

This report Environmental Environmental Triangle

represents

the

results

of work 68-02-4035

performed for the

by Northrop Methods

Services,

Inc. Branch,

Sciences under Monitoring

Contract

Development Agency,

Systems Laboratory,

U.S. Environmental

Protection

Research the

Park, NC. This work was conducted September 1984.

in response to Technical Directive 1.0-7 during

period April through

III

NORTHROP Environmental Sciences
ABSTRACT

TN-4120-85-03

Commercially

available Nafion tube dryers were tested for applications

of sample preparation

prior to gas chromatographic models, configurations, developed

analysis. Steady-state drying efficiency was measured for various dryer parameters at 95% relative humidity. was temporarily enhanced A procedure was of 20 as it with a

and experimental removal

in which water

efficiency

by a factor

compared to the steady state. dry sample stream immediately tested on an automated

This was accomplished

by heating the dryer while purging

prior to processing the gas sample of interest. system equipped of interest with

The procedure was a cryogenic no effect sample of this

gas chromatographic

preconcentrator.

Data for 15 volatile

organic compounds

showed

procedure on sample integrity;

some improvement

in run-to-run

precision was observed.

NORTHROP Environmental Sciences
SECTION 1 INTRODUCTION

TN-4120-85-03

The accurate identification at sub-parts per billion

and quantitation

of the many volatile organic compounds (VOCs) air generally requires performed preconcentration with of

by volume

levels in ambient

analytes to enhance instrument chromatographs

sensitivity.

Analyses are typically

high-resolution

coupled to appropriate

detectors (Holdren et al. 1985; Singh et al. 1979a,b; Cox and preconcentration is accomplished by passing

Earp 1982; Pellizzari et al. 1984b). whole air through gas chromatograph a cryogenic trap.

In this laboratory,

The sample is then thermally detection

desorbed into a capillary-column (ECD).

(GC) using flame ionization

(FID), electron capture detection

and/or mass selective detection

(MSD). The methodology

has been described elsewhere (McClenny

and Plei11984; McClenny et al. 1984; McClenny et al. 1985). Cryogenic particularly trapping has been shown to be a preferred preconcentration technique,

for the lighter

VOCs, i.e., C" C2, and C3 compounds

(McClenny et al. 1984; Pleil and

McClenny 1984; Cox et al. 1982; Rasmussen et al. 1977; Farwell et al. 1979; Des Marais 1978). These compounds are often tend to have low breakthrough used as preconcentration volumes on the solid sorbents (such as Tenax-GC) that

media (Singh 1979a,b; Pellizzari et al. 1984a,b; Bertsch et al. of ambient water vapor in a cryogenic trap while uSing the hydrophobic Tenax-Gc. of

1974; Pellizzari et al. 1976). However, the co-collection

can cause a number of problems that are not encountered Ice formation ambient during sample collection

can alter sample flow or clog the trap, the variability

water vapor can cause detector

baseline shifts, and co-collected water can cause blockage initial the

upon injection

onto the capillary column in separation techniques that require sub-freezing

GC oven temperatures.

In extreme cases, the excess water when eluted can even extinguish

hydrogen flame of an FID. Water-related problems can be alleviated by various methods. The simplest method is to the

reduce sampling volume, but this also reduces sensitivity.

Other techniques involve pre-drying

sample with various desiccants; however, these desiccants can affect sample integrity or outgassing some compounds. Also, dessicants are inconvenient

by adsorbing

to use because they require

periodic replacement

or reconditioning. a permeable membrane dryer commercially membrane available from Perma-Pure (E.I.

In this laboratory,

Products, Inc. (Farmingdale,

NJ) is used.

The permeable Dl), a copolymer

consists of Nafion tubing

Dupont de Nemours, Inc., Wilmington, monomer, through

of tetrafluoroethylene

and fluorosulfonyl

that is coaxially mounted within of the Nafion tubing;

larger tubing (Baker 1974). The sample stream is passed this allows water (and other light, polar compounds) to

the interior

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NORTHROP Environmental Sciences
permeate through the Nafion the walls into a dry air purge stream flowing (Kertzman

TN-4120-85-03

through the annular space between This is a constant for particular in the 1979;

and the outer tubing

1973; Perma-Pure Products, Inc.).

process that requires no maintenance. applications literature and its transmission

The Nafion dryer's water for specific

removal efficiency

efficiency

compounds

have been described

(Baker 1973; Kertzman

1973; Perma-Pure Products, Inc.; Foulger and Simmonds

Burns et at. 1983). The use of these dryers has already been validated and compounds of interest, i.e., selected light, nonpolar

for our sampling conditions and halogenated

hydrocarbons

hydrocarbons of environmental

concern (McClenny et at. 1984). data for different sizes and configurations of Nafion dryers. in is This

This paper presents performance

Experiments cover steady-state drying efficiencies and the time dependence of drying efficiency response to a step function in sample moisture content.

A novel dryer cleanup
portion

technique

presented that can be implemented technique temporarily

during the non-sampling

of a GC analysis cycle.

increased the water vapor removal efficiency

of the dryer by a factor of 20

over the steady-state efficiency and reduced system memory effects.

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NORTHROP Environmental Sciences
SECTION 2 EXPERIMENTAL

TN-4120-85-03

EQUIPMENT A number of different streams at flow dryer configurations are available from the manufacturer for drying air

rates of a few milliliters

per minute to more than 30 Umin.

The single-stranded of

models that cover the flow range up to approximately GC sample drying. The manufacturer's

200 ml/min were chosen for our application

model numbers and a physical description

of all dryers used in

this work are presented in Table 1. TABLE 1. NAFION TUBE DRYERS - AS PURCHASED FROM PERMA-PURE PRODUCTS, INC. Model No. MD-125-12(T) Physical Description 0.125 in. o.d.e Teflon purge tubing shell withpolypropylene length. Nafion tube: 0.12 cm o.d.; 0.065 cm l.d.>, fittings; 12 in.

MD-125-12(S)

0.125 in. o.d. 304 stainless steel purge tubing shell with stainless steel fittings and Viton o-ring seals; 12 in. length. Nafion tube: 0.12 cm o.d.; 0.065 cm i.d. 0.125 in. o.d. Teflon purge tubing shell with polypropylene length. Nafion tube: 0.12 cm o.d.; 0.065 cm i.d. fittings; 48 in.

M D-l 25-48(T)

MD-125-48(S)

0.125 in. o.d. 304 stainless steel purge tubing shell with stainless steel fittings and Viton o-ring seals; 48 in. length. Nafion tube: 0.12 cm o.d.; 0.065 cm i.d. 0.250 in. o.d. 304 stainless steel purge tubing shell with stainless steel fittings and Viton o-ring seals; 12 in. length. Nafion tube: 0.30 cm o.d.; 0.250 cm i.d.

MD-250-12(S)

a b

o.d. = outside diameter. i.d. = inside diameter.

Most dryer performance instrument is a prototype

data were obtained

with

an optical

water

vapor

monitor.

This

developed

under contract for the U.S. Environmental Corporation, Newport

Protection Agency by 1981).

Ford Aerospace and Communications Water vapor concentration in a flowing

Beach, CA (Burch and Goodsell by differential infrared

gas stream is determined

absorption

using bandpass filters centered at 2.51 and 2.59 11m. Sample cell volume is 56 cm3 and the detection limit is 10 parts per million water vapor concentration. by volume (ppmv) at 1 atm. Calibration The monitor curves cover ranges of up to 5% with known samples near

was spot checked periodically

100% relative humidity,

and measurements were compared to measurements of room air made by a

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NORTHROP Environmental Sciences
sling psychrometer and a calibrated hygrometer.

TN-4120-85-03

The monitor was extremely stable when sampling

zero gas and at the span settings. used, individual humidified efficiency,

For the various experiments in which the water vapor monitor was concentration measurements: outlet (5). dry zero air (Z), Percent dryi ng

data points consisted of three at dryer inlet

sample

(H), and dried

sample at dryer

E, was defined as E

= 100·[1-(5/H)].
with

Because Z, the baseline response, was always two or check on the water vapor temperature drifts that

three orders of magnitude monitor's stability.

less than 5, it was only used as a qualitative

Normalizing

H removed the effect of laboratory at the dryer inlet. instrumentation consisted

slightly affected the water vapor concentration In the final experiments, the analytical

of a fully

automated

sampling and analysis system that included an HP-5880 Level 4 GC (Hewlett-Packard, and a modified Nutech 320-1 cryogenic trapping and desorption

Avondale, PA)

unit (Nutech Corp., Durham, NC). (Tylan Corp., Carson, CA). For

All critical gas flows were regulated some tests, a quadrupole detector for water. PERFORMANCE SURVEY EXPERIMENTS

by Tylan mass flow controllers

mass spectrometer

(HP-5970 M5D, Hewlett-Packard)

was used as a GC

Initial experiments

consisted of a survey of drying performance at room temperature,

of five different

dryer models were

(see Table 1). All tests were performed used to set and maintain respectively. water impinger plumbing. Humidified

and Tylan mass flow controllers air) at 50 ml/min

sample and purge flow (zero-grade sample (at 95% relative humidity) Teflon tubing

and 250 mllmin, a 500-ml

was generated and fittings

by inserting

flask into the sample stream.

were used for all gas flow

For each dryer in the initial survey, the steady-state drying efficiency was determined the method described earlier. zero air could flow through The humidifier

by using

was then removed from the sample stream so that dry

the interior of the Nafion dryer, and the dryer was heated to 100°C. The at the dryer outlet to reach a zero baseline, i.e., for any After the dryer had cooled to room temperature, the

time, Td, needed for the sample humidity

residual water to be removed, was recorded.

zero baseline was accurately measured and the humidifier The time, T u, required for the sample humidity state value was recorded. were used to initially The.following

was reinserted into the sample stream.

at the dryer outlet to increase to 10% of the steadysteady-state drying efficiency, Td, and Tu

three parameters:

characterize the various models. REPEATABILITY were then performed: efficiency the series/parallel test. purge gas

PURGE FLOW DEPENDENCE AND PERFORMANCE Three sets of more detailed test, the purge flow dependence experiments

test, and the drying

precision

Because these

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NORTHROP Environmental Sciences
experiments were very time consuming, only those dryers of immediate

TN-4120-85-03

interest for our specific

applications were tested. Two dryers each of model descriptions) efficiency numbers MD-125-48(T) and MD-125-12(S) (see Table 1 for

were tested in pairs in either a series or parallel configuration purge flow.

for steady-state drying zero air. For

with a 500-ml/min

Sample flow was 50 mllmin of humidified using a 500-ml/min purge flow.

comparison, dryers were also tested individually flow arrangement series configuration

Figure 1 shows the

for each case. In each configuration

the same total purge flow was used. The acts as two with

essentially lengthens a single dryer. The parallel purge configuration

separate dryers; the second further dries the sample output of the first. Flows were maintained mass flow controllers.

In the second set oftests, one MD-250-12(S) and four MD-125-48(T) dryers were used. Steadystate drying efficiency was determined for a 50-ml/min humidified zero air sample stream as a

function of dryer purge flow; a range of 200 to 1250 mllmin was used for the 1/8 in. outside diameter MD-125-48(T) dryers, and additional diameter MD-250-12(S) dryer. settings up to 3500 mllmin were used for the larger outside

Mass flow controllers were used to supply consistent purge flows. All

flows were periodically

audited with a bubble flow meter. used four MD-125-48(T) dryers. Steady-state drying efficiency a one-month testing

The third set of experiments was independently period. content

measured for each dryer at various times throughout that ranged from 19 to 24°C caused variation inlet. Humidified sample flow

Room temperatures

in the absolute water were

of the sample at the dryer

and dry purge flow

maintained

at 50 and 250 ml/min, respectively.

Flows were periodically

audited with a bubble flow

meter to ensure consistency over this extended testing period. DRYER CLEANUP PROCEDURE EXPERIMENTS Previous work had demonstrated that the permeable membrane of the dryers, Nafion tubing, heat and substituting pure gas for the sample flow

could be successfully cleaned by applying (McClenny treatment

etal. 1984). A final set of experiments was performed to determine the effects of such
on dryer performance under actual sampling conditions.
In

Typically, an ambient collection instrument run-to-run

air analysis

our laboratory

consists of three distinct phases: sample column (30 min); and

using a cryogenic trap (15 min); GC analysis using a capillary resetting, report printing, precision is determined

etc. (15 min). This procedure is fully automated

and repetitive;

primarily by the sample. Because sample drying is only necessary clean up air

for 15 min out of the total analysis time of 60 min, a procedure was devised to automatically the dryer during its idle time.

This procedure involved flushing the dryer with dry zero-grade

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NC)RTHRDP Environmental Sciences
A

TN-4120-8S-03

---------------------------------Vent

Dryer

Monitor

----------------------------------

B

Dryer 1

Dryer 2

c
250 ml/min Dryer 1 250 ml/min Dryer 2

_________

.....a

Figure 1. Arrangement for measuring steady-state drying performance of various dryer configurations: (A) single dryer, (B) series purge-gas configuration, and (C) parallel purge-gas configuration. The flow of dry zero gas is regulated with two massflow controllers (MFC).

7

NORTHROP Environmental Sciences

TN--:'4120-85-03

while the dryer was heated to 100"C. It was then allowed to cool to room temperature sample collections.

between

The MD~125-48(T) dryer (currently in use on the instrument) was wrapped with aluminum foil, heating tape, and insulation. transformer through The heating tape was wired through temperature). a solid state relay to a variable valve, also wired Both relays were is

(used to set a maximum

A solenoid gas switching

a relay, was installed at the dryer inlet to select either sample or dry air. activation. A diagram

connected to the GC to allow computer-controlled shown in Figure 2. The appropriate programming

of this arrangement automated repetitive

was installed to allow

analysis with or without

the cleanup procedure.

A number of experiments were then performed to

evaluate the new method.

le--"·


""

Manifold

Sample ,..--------.... "...

Dryer and Heater
"

Analytical System

~-~~~~"~.~"~."~.~.~.~"~~~~

Zero Air

Computer

Heater Relay--

.........

Valve Relay Variable Transformer

Relay Control Signals
Figure 2. Schematic diagram of automated dryer cleanup procedure. When valve relay is off, valve is closed and sample is pulled from manifold. When valve relay is activated, valve is open and zero air overfills dryer inlet and displaces manifold sample. Heater relay can then be activated to apply pre-set voltage from variable transformer to heat the dryer. In the first set of experiments, the mass spectrometer was used as the GC detector. The system

was set up to display the elution of 18 atomic mass units (amu) fragments, the parent ion for water. A humidified sample. zero air stream at a flow rate of 2 Umin introduced into a glass manifold was the

Four consecutive

analyses were then performed

using the described cleanup procedure;

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NORTHROP Environmental Sciences
these were followed dryer was thoroughly by four analyses without the procedure.

TN-4120-85-03

Before each set of four analyses the

purged of all residual water.

A second set of experiments was performed to determine the dependence of drying efficiency on time during such cleanup cycles. The water vapor monitor was inserted into the sample stream between the dryer and the analytical system (refer to Figure 2). The analytical procedure used in the first set of experiments was repeated while the water content at the dryer outlet was monitored. In the third set of experiments, tested. The water vapor monitor the effect of the cleanup procedure on sample integrity were removed from was

and the mass spectrometer calibration

the system.

Simultaneous within

FID and ECDwere used. A flowing

mixture of 15 compounds of interest, all

the concentration

range of 8 to 12 parts per billion by volume (ppbv) In humid zero air, was 2 Umin. Seven consecutive analyses without the procedure. After each

established in the glass manifold at a flow rate of approximately were performed

with the cleanup procedure, and seven were performed

These two sets of runs were performed set, humidified

on consecutive days under identical conditions.

zero air was sampled to determine residual contamination.

9

NORTHROP Environmental Sciences
SECTION 3 RESUl TS AND DISCUSSION

TN-4120-85-03

As presented in Table 2, the initial survey of various types of dryers showed consistent drying efficiencies 50 ml/min; purge flow corresponds of about 80% for our conditions: dry purge flow rate of 250 ml/min. humidity 95% relative humidity of the sample and a flow rate of between sample and dryer). This

This suggests that an equilibrium less than

was reached at a dryer length

12 in. (the shortest here, lowering

to a residence time of 0.12 s. Though undocumented also lowers the product humidity;

the incoming

sample humidity

however, resultant drying efficiencies can be less

than 80%. This behavior has been documented

elsewhere (Baker 1974, Foulgar and Simmonds 1979;

Burns et al. 1983). All drying efficiencies presented here are based on an incoming sample stream at about 95% relative humidity to anticipate worst-case conditions for ambient sampling.

TABLE 2. RESULTS OF INITIAL PERFORMANCE SURVEY OF VARIOUS MODelS OF DRYERSa

Eb
Model No. MD-125-12(T) MD-125-12(S) M D-12 5-48(T) MD-125-48(S) MD-250-12(S)
a b c d

(percent) 80 82 81 80 82

Tdc (min) 80 80 70 75 170

Tud (min) 2 2 23 23 11
room temperature.

Test conditions: Steady-state Timeto

SO-ml/min humid sample flow;

2S0-ml/mln dry purge gas flow;

drying efficiency.

Time to purge residual water. reach 10% of E.

The time dependence The time required

of dryer performance residual water

varied greatly with configuration a dryer starting

(see Table 2). conditions The longer

to remove

from

at steady-state

essentially depended on the outside diameter dryers had a slightly

of the Nafion tubing,

not on the length.

shorter purge time requirement.

Thus, it appears that residual water removal The time shows

depends on the amount of Nafion tubing per length rather than on total material present. required for a dryer to reach 10% of its steady-state value when starting totally period during which drying efficiency is greatly

dehydrated

that there is an initial increase in length improved

enhanced.

Here, both an

and an increase in the Nafion tubing's

outside diameter

increased this time of

performance.

These results indicate an initial condition appreciable permeation

in which water is absorbed by the However, once the humidity

Nafion tubing without

into the purge stream.

10

NORTHROP Environmental Sciences

TN-4120-8s-03

gradient across the Nafion membrane becomes established, the water removal rate becomes limited by the uptake Although capacity of the purge gas and the water permeation rate through the Nafion.

this could not be measured directly, the explanation

is consistent with our experiments.

The purpose of the purge gas configuration arrangement. would

test was to determine the effects of a dual dryer combination the parallel than

Total purge flow was set at 500 mllmin in all tests so that a two-dryer to previous tests. The results, shown in Table 3, show that

be comparable

configuration

was more efficient

than a series configuration diagrams).

which, in turn, was more efficient

a single dryer (see Figure 1 for configuration efficiency, however, do not appear

The relatively small improvements of an extra dryer.

in drying

to warrant

the addition

The parallel equilibrium

configuration's

superior performance

reinforces the earlier observation that a humidity

is reached quickly, i.e., that added dryer length is less effective than removing accumulated water in the purge gas. temperatures These tests were performed with samples at 95% relative humidity and at room

to anticipate

worst-case ambient conditions.

TABLE 3. DRYING EFFICIENCIES FOR DRYERS UNDER VARIOUS PURGE FLOW CONFIGURATIONSa

EC
Model No. MO-125-12(S) Configurationb Single Series Parallel Single Series Parallel
humid sample flow; 500-ml/mln total purge flow; room temperature.

(percent) 85.3 86.6 89.0 87.9 88.4 94.9

M 0-1 25-48(T)

a b c

Test conditions: Steady-state

50-ml/min

Refer to Figure 1 for flow diagrams. drying efficiency.

Table 4 shows that increasing the purge gas flow resulted in an increase in drying efficiency, E. This relationship respectively. humidified. is approximately E = l-(SF/PF), where SFand PFdenote sample flow and purge flow, at purge flows at or below 500 mllmin when the sample is highly that 500 mllmin was a reasonable upper limit for the 1/8 in. outside

It is appropriate (It was determined

diameter dryers.) At higher purge flows, drying efficiency approached an upper limit of about 89% for our particular conditions. There was very little difference between the MD-125-48(T) and MO-

250-12(5) dryers other than the option of increased purge flow. The last test of this series was performed these dryers. Results of 17 independent to determine the ove-rall stability in performance of

tests to measure steady-state dryi ng efficiency of 0.84. All four MD-125-48(T)
In

showed a

mean of 80.83% and a standard deviation identically

dryers were treated

in this test even though two had been used

our laboratory

for about two years and the

i1

I','

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NPRTHRDP Environmental Sciences
other two had just been purchased. These encouraging Individual dryers showed no appreciable

TN-4120-8S-03

bias in drying can be

efficiency.

results indicate that individual

dryers of the same model

considered interchangeable

and that prolonged

use does not appear to degrade performance.

TABLE 4. DRYING EFFICIENCIES USING VARIOUS PURGE FLOWSa Eb (percent) MD-125-48(T) 7S.2 80.8 MD-2S0-12(S) 79.2 81.6 82.6 87.9 87.4 88.3 89.1 89.1 89.5
room temperature.

Purge Flow (ml/min) 200 2S0 360 500 660 1,250 2,400 3,SOO
a. Test conditions: b

SO-ml/mm humid sample flow;

Steady-state

drying efficiency.

As noted earlier, a fully dehydrated when a humidified

dryer exhibited

a temporary

increase in drying efficiency allowed about the dryer. period The of

sample was first introduced.

Because our sampling requirements

45 min of down time between sample collections, we used this time to recondition MD-12S-48(T) dryer was chosen for this set of tests because it exhibited enhanced performance of experiments

the longest

(see the Tu parameter in Table 2), as well as a reasonable purge time.

Results

to test the automated

cleanup system (see Figure 2) showed that it greatly reduced system as compared to using the dryer under steady-state as the GC detector) are presented in

the water introduced conditions. Qualitative

into the analytical

results (using the mass spectrometer

Figure 3, in which the eluting without the cleanup cycle.

water vapor peak is shown for three consecutive GC runs with and of eluting water was constant from run to run when the when the cleanup procedure was not used. because steady-state

The amount

cleanup procedure was used, but increased dramatically This experiment could not be used to quantify

water removal improvements

dryer use (as reached after the fourth run) allowed so much water into the analytical system that the detector overloaded.

12

NORTHROP Environmental Sciences
A

TN-4120-85-03

~J
~

/!

Ii

B

-----c==:::::

'/i

....

,
:

/'

/ ,

:

,
I I

:

~

Time

-

/
~

I ,

-=
, ,

I I I

Time

Figure 3. Two sequences of three consecutive GC runs showing the elution of the 18 amu fragment (parent ion o+water) as measured by the mass spectrometric detector: (A) with interim dryer cleanup procedure and (B) without interim dryer cleanup procedure. In each case, the dryer was initially dehydrated. The drying improvement water vapor monitor. caused by the automated cleanup system was measured with the

The water content of the sample stream as it entered the analytical system is graphs of water monitor response versus time that are sampling

presented in Figure 4 as two overlapping annotated to indicate the sampling

periods.

These curves correspond to four complete

cycles for both drying procedures, i.e., with and without temperature, the monitor. analytical the area under the curves is proportional Careful study has shown a typical when the cleanup procedure

interim cleanup. When the dryer is at room to the total amount of water passing through in water removal for our

20-fold improvement is used.

conditions

This is illustrated

in Figure 4 by an

expanded view of one sample collection Results for the final characterized calibration calibration experiment,

portion of these curves. in which the cleanup procedure was used on wellcompounds in the

samples, are presented those eluting

in Table 5.

The individual

mixture,

particularly

late, tended to equilibrate

throughout

the day. This

sample concentration did not permit

drift during the tests was unavoidable prior to each experiment.

because time and resource constraints based on regression

equilibration

Thus, the data were compared The calculated

linear regressions of peak area versus run number for each compound.

13

NORTHROP
Environmental Sciences

TN-4120-85-03

Sample Water Content

A
Collect: Sample:

B

• Purge': Dryer
I

Time-r-~".

Figure 4. Sequence of four consecutive GC runs showing water monitor response versus time as measured at the dryer outlet just prior to entering the GC: (A) with interim dryer cleanup procedure and (B) without interim dryer cleanup procedure. Expanded view of the sample collection portion of the analytical cycle depicts reduction in injected water vapor. The heavily shaded region is proportional to the amount of water collected with the sample when the dryer is pretreated; the lighter shaded area beneath the steady-state line is proportional to water collected without dryer pretreatment. Sample content at dryer inlet (95% relative humidity at room temperature) would be far off the scale in this graph. slope is a combination of overall sample concentration drift and any run-to-run memory effects in

the system. For the FID data, the cleanup procedure exhibited a consistently lower area/run number drift. The ECDdata showed no consistent differences. To determine. the effect of the dryer cleanup on system precision, the root difference compound. between the regression curve and the individual mean square for each

data points was calculated

These values are expressed as a percentage

of the mean peak area to facilitate

comparisons among compounds and among detectors and to determine whether or not the cleanup

Envll'onmental Sciences

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TABLE 5. COMPARISON STATISTICS FOR SEVEN ANALYSIS RUNS WITH AND WITHOUT THE INTERIM DRYER CLEANUP PROCEDUREa Regression Siopeb (area/run no.) Compound FlO Vinyl chloride Vinylidene chloride ,2,21,1,2- Trichloro-l trifl uoroethane Chloroform 1,2-Dichloroethane Methyl chloroform Carbon tetrachloride Trichloroethylene 1,3-Dichloropropene 0.104 -0.098 0.036 0.029 0.081 0.073 -0.003 0.111 0.075 0.076 0.038 0.120 0.389 0.831 iene ,2,20.619 389 287 984 2,045 444 9,011 9,274 7,419 -0.040 -0.105 -0.155 0.114 0.275 0.052 0.076 0.326 0.298 0.308 0.646 0.426 1.418 2.917 1.773 -564 110 -3,799 -2,836 539 570 639 18,751 1.52 1.48 1.87 1.45 0.84 0.77 1.34 0.83 0.81 0.93 1.06 0.73 1.06 1.49 1.12 0.23 0.35 0.13 0.27 0.51 4.78 3.06 2.40 2.16 2.95 1.20 3.79 1.40 1.16 6.53 1.28 1.54 5.53 1.49 2.26 3.50 6.36 2.92 1.30 1.46 4.17 1.20 2.83 4.31 5.26 2.24 Cleanup No Cleanup RMS Residualc (percent) Cleanup No Cleanup

-cis -trans
1,2-Dibromoethane Tetrachl oroethyl ene Chlorobenzene Benzyl chloride Hexach Iorobutad ECD 1,1,2- Trichloro-l trifl uoroethane Chloroform Methyl chloroform Carbon tetrachloride Trichloroethylene 1,2-Dibromoethane Tetrach Ioroethyl ene Hexachlorobutadiene
a

b

C

Target compounds ranged from 8 to 12 ppbv in humidified zero-grade air. Samples were collected at 34 ml/rnin for 14 min into a cryotrap maintained at -155°C. Least squares linear regression slope of peak area vs. run no. for seven consecutive analyses either with or without the dryer cleanup procedure. For FID, mean areas ranged from 5 to 55; for ECD,mean areas ranged from 100,000 to 1,000,000. Root mean square difference between calculated linear regression curve and ind.vidual data points; normalized to a percentage of the mean peak area for the particular compound.

procedure procedure

was used. was used.

Data from

the FID showed

consistently

lower

scatter residuals.

when

the cleanup when in

The ECD data showed either lower or equivalent of temporary column

In addition,

the procedure

was not used, one instance

blockage

and another

instance

15

NOHtHRO'P Environmental Sciences
which the FlO flame was extinguished were encountered.

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These occurrences were attributed

to

excess accumulated

water; this was confirmed

in similar tests using the mass spectrometer. runs showed little or no

Finally, the zero air run performed contamination

after the set of seven calibration

when the cleanup procedure was used. Residual peaks of about 0.1 to 0.3 ppbv each tetrachloroethylene, benzyl chloride, and hexachlorobutadiene were

for carbon tetrachloride,

observed when the interim cleanup procedure was not used.

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N~RTHRDP Environmental Sciences
SECTION 4 CONCLUSIONS

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From the experiments

presented here some general conclusions can be made about the use of sample conditioning. flow Dryer models should be chosen for Steady-state drying response

Nafion tube dryers for chromatographic their physical attributes

(i.e., size requirements,

considerations). models.

performance is important,

tends to be similar for the various single-stranded

If time-dependent

dryer models should be chosen based on the Nafion tube configuration.

Equilibration

time from a dehydrated

state to steady-state performance tends to scale with length, whereas purge

time (necessary to dehydrate the dryer at 100°C) tends to scale with the amount of Nafion tubing per length. Drying efficiency can be improved by increasing purge flow; however, the point of

diminishing

returns is reached fairly quickly.

In our very restricted sample set, essentially no variation in performance of dryers used

in performance

among dryers of the same type and no degradation

daily over a period of two years were observed. Drying efficiency can be greatly improved for a short time by first processing the dryer with a to approximately 100°Cto drive out any residual water.

dry sample flow and raising the temperature In our experiments, 20 over steady-state

water removal during short sampling periods could be increased by a factor of operation. Such a procedure does not effect sample integrity, at least for all

15 compounds tested here, and tends to reduce memory effects from previous samples. This cleanup procedure ambient is particularly useful for our application, cryogenic preconcentration water of VOCs from and

air for subsequent

GC analysis, because excess accumulated

can cause trap

column blockage and also adversely affect detector precision.

In addition, the improvement

in water

removal will allow sampling of much larger volumes of ambient air in the event that greater system sensitivities to compounds of interest are required.

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SECTION 5 REFERENCES

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Baker, B.B. 1974. Measuring trace impurities in air by infrared spectroscopy at 20 meters path and 10 atmospheres pressure. Am. Ind. Hyg. Assoc. 1. November pp.735-740. Bertsch, W., R.C. Chang, and A. Ziatkis. 1974. The determination of organic volatiles in air pollution studies: Characterization of profiles. 1. Chromatogr. Sci. 12: 175-182. Burch, D.E. and D.S. Goodsell. 1981. Development of an H20 monitor using differential infrared absorption. U.S. EPA Final Report (EPA-600/2-81-162) on Contract 68-02-3238 to Ford Aerospace and Communications Corporation. Research Triangle Park, NC: U.S. Environmental Protection Agency. Burns, W.F., D.T. Tingey, R.C. Evans, and E.H. Bates. 1983. Problems with a Nafion membrane dryer for drying chromatographic samples. J. Chromatogr. 269: 1-9. Cox, R.D. and R.F. Earp. 1982. Determination of trace level organics in ambient air by highresolution gas chromatography with simultaneous photoionization and flame ionization detection. Anal. Chem. 54:2265. Cox, R.D., M.A. McDevitt, K.W. Lee, and G.K. Tannahill. 1982. Determination of low levels of total non-methane hydrocarbon content in ambient air. Environ. Sci. Techno/. 16:57-61. Des Marais, D.J. 1978. Variable Anal. Chem. 50: 1405-1406. temperature cryogenic trap for the separation of gas mixtures.

Farwell, S.O., S.J. Gluck, W.L. Bamesberger, T.M. Schuttle, and T.F. Adams. 1979. Determination of sulfur containing gases by a deactivated cryogenic enrichment and capillary gas chromatographic system. Anal. Chem. 51: 609-615. Foulger, B.E. and P.G. Simmonds. gases. Anal. Chem. 51: 1089. 1979. Drier for field use in the determination of trace atmospheric

Holdren, M., S. Rust, R. Smith, and J. Koetz. 1985. Evaluation of cryogenic trapping as a means for collecting organic compounds in ambient air. U.S. EPA Final Report (EPA-600/4-85-002) on Contract 68-02-3487 to Battelle Columbus Laboratories. Research Triangle Park, NC: U.S. Environmental Protection Agency. Kertzman, J. 1973. Continuous drying of process sample streams. of America, Analytical Instrumentation Division. Paper 73425. Instrument Society

McClenny, W.A. and J.D. Pleil. 1984. Automated calibration and analysis of VOCs with a capillary column gas chromatograph equipped for reduced temperature trapping. Paper 84-17.6. Proceedings of the 77th APCA Meeting, San Francisco, CA, June 24-29. McClenny, W.A., J.D. Pleil, M.W. Holdren, and R.N. Smith. 1984. Automated cryogenic preconcentration and gas chromatographic determination of volatile organic compounds in air. Anal. Chem. 56:2947.

NORTHROP Environmental Sciences
McClenny, W.A., J.D. Pleil, K.D. Oliver, and M.W. Holdren. 1985. Comparison oftwo compounds monitors equipped with cryogenic preconcentrators. 1. Air Po/lut. 35 (10): 1053-1056.

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volatile organic Control Assoc.

Pellizzari, E.D., J.E. Bunch, R.E. Berkeley, and J. McRae. 1976. Determination of trace hazardous organic vapor pollutants in ambient atmospheres by gas chromatography/mass spectrometry/computer. Anal. Chem. 48:803-806. Pellizzari, E., B. Demian, and K. Krost. 1984a. Sampling of organic reactive inorganic gases with Tenax GC. Anal. Chem. 56:793-798. compounds in the presence of

Pellizzari, E.D., W.F. Gutknecht, S. Cooper, and D. Hardison. 1984b. Evaluation of sampling methods for gaseous atmospheric samples. U.S. EPA Final Report on Contract No. 68-02-2991 to Research Triangle Institute. Research Triangle Park, NC: U.S. Environmental Protection Agency. Perma-Pure Products, Inc. Bulletin 106. Farmingdale, NJ.

Pleil, J.D. and W.A. McClenny. 1984. Temperature-dependent collection efficiency of a cryogenic trap for trace-level volatile organic compounds. Paper 84-17.5. Proceedings of the 77th APCA Meeting, San Francisco, CA, June 24-29. Rasmussen, R.A., D.E. Harsch, P.H. Sweany, J.P. Krasnec, and D.R. Cronn, 1977. Determination of atmospheric halocarbons by a temperature-programmed gas chromatographic freezeout concentration method. L Air Pollut. Control Assoc. 27: 579-581. Singh, H.B., L.J. Salas, H. Shigeishi, and E. Scribner. 1979a. Atmospheric and SF6: Global distributions, sources, and sinks. Science 203:899. halocarbons, hydrocarbons,

Singh, H.B., LJ. Salas, R. Stiles, and H. Shigeishi. 1979b. Measurements of hazardous organic chemicals in the ambient atmosphere. U.S. EPA Final Report on Cooperative Agreement 805990 to SRI International. Research Triangle Park, NC: U.S. Environmental Protection Agency.

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