P.1 

OAR Box 1107 

Prepped by Ollie Stewart 

Document Number: 

AA) IV-A-3 

Docket Number: 

A-81-21 

Printed 4/11/2008 3:03:46 PM Sheet 44 of 90 
trb 

United Stales 

Environmental Protection 

Agency 

Env 

Supp( 

Cincir 

D( ^ — * *— » * 

P.2 

IV-A-3 

Research and Development 

Test Method 

Purgeable Halocarbons 

Method 601 

1. Scope and Application 

1.1 This method covers the determination of 29 purgeable halocarbons. 

The following parameters may be 

determined by this method: 

Parameter 

Bromodichloromethane 

Bromoform 

Bromomethane 

Carbon tetrachloride 

Chlorobenzene 

Chloroethane 

2-Chloroethylvinyl ether 

Chloroform 

Chloromethane 

Dibromochloromethane 

1,2-Dichlorobenzene 

1,3-Dichlorobenzene 

1,4-Dichlorobenzene 

Dichlorodifluoromethane 

1,1 -Dichloroethane 

1,2-Dichloroethane 

1,1-Dichloroethene 

trans-1,2-Dichloroethene 

1,2-Dichloropropane 

cis-1,3-Dichloropropene 

trans-1,3-Dichloropropene 

Methylene chloride 

1,1,2,2-Tetrachloroethane 

Tetrachloroethene 

1,1,1 -Trichloroethane 

1,1,2-Trichloioethane 

Trichloroethene 

Trichlorofluoromethane 

Vinyl chloride 

STORET No. 

3210 1 

3210 4 

3441 3 

3210 2 

3430 1 

3431 1 

3457 6 

3210 6 

3441 8 

3210 5 

3453 6 

3456 6 

3457 1 

3466 8 

3449 6 

3453 1 

3450 1 

3454 6 

3454 1 

3470 4 

3469 9 

3442 3 

3451 6 

3447 5 

3450 6 

345 1 1 

3918 0 

3448 8 

3917 5 

CAS No. 

75-27- 4 

75-25-2 

74-83-9 

56-23- 5 

108-90-7 

7 5-00-3 

100-75-8 

67-66- 3 

74-87- 3 

124-48-1 

95-50-1 

541-73- 1 

106-46-7 

75-71- 8 

75-34- 3 

107-06-2 

75-35- 4 

156-60-5 

78-87- 5 

10061-01- 5 

10061-02- 6 

75-09-2 

79-34-5 

127-18- 4 

71-55-6 

79-00- 5 

79-01- 6 

75-69- 4 

75-01- 4 

1.2 This is a purge and trap gas 

chromatographic method applicable to 

the determination of the compounds 

listed above in municipal and industrial 

discharges as provided under 4 0 CFR 

601-1 July 1982 

136.1 . When this method is used to 

analyze unfamiliar samples for any or 

all of the compounds above, compound 

identification should be supported by at 

least one additional qualitative 
P.3 

technique. This method describes 

analytical conditions for a second gas 

chrqmaton.r'aphic column that can be 

used to confirm measurements made 

with the piimary column. Method 62 4 

provides gas chromatograph/mass 

spedrometer (GC/MS) conditions 

appropriate for the qualitative and 

quantitative confirmation of results for 

most of the parameters listed above. 

1.3 The method detection limit (MDL, 

defined in Section 1 2.1 )H) for each 

parameter is listed in Table 1. The MDL 

for a specific wastewater may differ 

from those listed, depending upon the 

nature of interferences in the sample 

matrix. 

1.4 Any modification of this method, 

beyond those expressly permitted, 

shall be considered as major modifications subject to application and 

approval of alternate test procedures 

under 4 0 CFR 136. 4 and 136.5 . 

1.5 This method is restrictedto use 

by or under the supervision of analysts 

experienced in the operation of a purge 

and trap system and a gas chromatograph and in the interpretation of 

chromatograms. Each analyst must 

demonstrate the ability to generate 

acceptable results with this method 

using the procedure described in 

Section 8.2. 

2. Summary of Method 

2.1 An inert gas is bubbled through a 

5-mL water sample contained in a 

specially-designed purging chamber at 

ambient temperature. The halocarbons 

are efficiently transferred from the 

aqueous phase to the vapor phase. The 

vapor is swept through a sorbent trap 

where the halocarbons are trapped. 

After purging is completed, the trap is 

heated and backflushed with the inert 

gas to desorb the halocarbons onto a 

gas chromatographic column. The gas 

chromatograph is temperature programmed to separate the halocarbons 

which are then detected with a halidespecific detector.<2

-

3

> 

2.2 The method provides an optional 

gas chromatographic column that may 

be helpful in resolving the compounds 

of interest from interferences that may 

occur. 

3.. Interferences 

3.1 Impurities in the purge gas and 

organic compounds out-gassing from 

the plumbing ahead of the trap account 

for the majority of contamination 

problems. The analytical system must 

be demonstrated to be free from 

contamination under the conditions of 

the analysis by running laboratory 

reagent blanks as described in Section 

8.5. The use of non-TFE plastic tubing, 

non-TFE thread sealants, or flow 

controllers with rubber components in 

the purging device should be avoided. 

3.2 Samples can be contaminated by 

diffusion of volatile organics (particularly fluorocarbons and methylene 

chloride) through the septum seal into 

the sample during shipment and 

storage. A field reagent blank prepared 

from reagent water and carried through 

the sampling and handling protocol can 

serve as a check on such 

contamination. 

3.3 Contamination by carry-over can 

occur whenever high level and low 

level samples are sequentially analyzed. 

To reduce carry-over, the purging 

device and sample syringe must be 

rinsed with reagent water between 

sample analyses. Whenever an 

unusually concentrated sample is 

encountered, it should be followed by 

an analysis of reagent water to check 

for cross contamination. For samples 

containing large amounts of watersoluble materials, suspended solids, 

high boiling compounds or high 

organohalide levels, it may be necessary to wash out the purging device 

with a detergent solution, rinse it with 

distilled water, and then dry it in a 

1 0 5 °C oven between analyses. The 

trap and other parts of the system are 

also subject to contamination; therefore, frequent bakeout and purging of 

the entire system may be required. 

4. Safety 

4.1 The toxicity or carcinogenicity of 

each reagent used in this method has 

not been precisely defined; however, 

each chemical compound should be 

treated as a potential health hazard. 

From this viewpoint, exposure to these 

chemicals must be reduced to the 

lowest possible level by whatever 

means available. The laboratory is 

responsible for maintaining a current 

awareness file of OSHA regulations 

regarding the safe handling of the 

chemicals specified in this method. A 

reference file of material data handling 

sheets should also be made available to 

all personnel involved in the chemical 

analysis. Additional references to 

laboratory safety are available and 

have been identified! 4 6 1 for the information of the analyst. 

4.2 The following parameters 

covered by this method have been tentatively clfcssified as known or 

suspected, human or mammalian 

carcinogens: carbon tetrachloride, 

chloroform, 1,4-dichloiobenzene, and 

vinyl chloride. Primary standards of 

these toxic compounds should be 

prepared in a hood. A NIOSH/MESA 

approved toxic gas respirator should be 

worn when the analyst handles high 

concentrations of these toxic 

compounds. 

5. Apparatus and Materials 

5.1 Sampling equipment, for discrete 

sampling. 

5.1.1 Vial —25-mL capacity or larger, 

equipped with a screw cap with hole in 

center (Pierce #1 307 5 or equivalent). 

Detergent wash, rinse cap with tap and 

distilled water, and dry at 105 °C 

before use. 

5.1.2 Septum —Teflon-faced silicone 

(Pierce #1272 2 or equivalent). 

Detergent wash, rinse with tap and 

distilled water, and dry at 1 05 °C for 

one hour before use. 

5.2 Purge and trap device —The 

purge and trap device consists of three 

separate pieces of equipment: the 

sample purger, trap, and the desorber. 

Several complete devices are now 

commercially available. 

5.2.1 The sample purger must be 

designed to accept 5-mL samples with 

a water column at least 3 cm deep. 

The gaseous head space between the 

water column and the trap must have a 

total volume of less than 1 5-mL. The 

purge gas must pass through the water 

column as finely divided bubbles with a 

diameter of less than 3 mm at the 

origin. The purge gas must be introduced no more than 5 mm from the 

base of the water column. The sample 

purger, illustrated in Figure 1, meets 

these design criteria. 

5.2.2 The trap must be at least 25 

cm long and have an inside diameter of 

at least 0.1 0 5 inch. The trap must be 

packed to contain the following 

minimum lengths of adsorbents: 1.0 

cm of methyl silicone coated backing 

(Section 6.3.3), 7.7 cm of 

2,6-diphenylene oxide polymer 

(Section 6.3.2), 7.7 cm of silica gel, 

7.7 gm of coconut charcoal (Section 

6.3.1). If it is not necessary to analyze 

for dichlorodifluroromethane, the charcoal can be eliminated, and the polymer 

section lengthened to 1 5 cm. The 

minimum specifications for the trap are 

illustrated in Figure 2. 

5.2.3 The desorber must be capable 

of rapidly heating the trap to 1 80 °C. 

The polymer section of the trap should 

601-2 July 1982 
P.4 

not be heated higher than 1 80 °C and 

the remaining sections should not 

exceed.220 °C. The desorber design, 

illustrated in Figure 2, meets these 

criteria. 

5.2.4 The purge and trap device may 

be assembled as a separate unit or be 

coupled to a gas chromatograph as 

illustrated in Figures 3 and 4. 

5.3 Gas chromatograph —An analytical system complete with a temperature programmable gas chromatograph 

suitable for on-column injection and all 

lequired accessories including syringes, 

analytical columns,, gases, detector, 

and strip-chart recorder. A data system 

is recommended for measuring peak 

areas. 

5.3.1 Column 1- 8 ft long x 0.1 in 

ID stainless steel or glass, packed with 

1 % SP-1 00 0 on Carbopack B (60/80 . 

mesh) or equivalent. This column was 

used to develop the method performance statements in Section 1 2. 

Guidelines for the use of alternate 

column packings are provided in 

Section 10.1 . 

5.3.2 Column 2- 6 ft long x 0.1 in 

ID stainless steel or glass, packed with 

chemically bonded n-octane on PorasilC (100/1 20) mesh or equivalent. 

5.3.3 Detector—Electrolytic conductivity or microcoulometric. These types 

of detectors have proven effective in 

the analysis of wastewaters for the 

parameters listed in the scope. The 

electrolytic conductivity detector was 

used to develop the method performance statements ^nd MDL listed in 

Tables 1 and 2. Guidelines for the use 

of alternate detectors are provided in 

Section 10.1 . 

5.4 Syringes—5-mL glass hypodermic with Luerlok tip (two each), if 

applicable to the purging device. 

5.5 Micro syringes—25 pL, 0.00 6 in 

ID needle. 

5.6 Syringe valve —2-way, with Luer 

ends (three each). 

5.7 Syringe—5-mL, gas-tight with 

shut-off valve. 

5.8 Bottle—1 5-mL, screw cap, with 

Teflon cap liner. 

5.9 Balance —Analytical, capable of 

accurately weighing 0.000 1 g. 

6. Reagents 

6.1 Reagent water— Reagent water is 

defined as a water in which an 

interferent is not observed at the MDL 

of the parameters of interest. 

6.1.1 Reagent water can be generated 

by passing tap water through a carbon 

filter bed containing about 1 Ib. of 

activated carbon (Filtrasorb-300 or 

equivalent (Calgon Corp.)). 

6.1.2 A water purification system 

(Millipore Super-Q or equivalent) may 

be used to generate reagent water. 

6.1.3 Reagent water may also be 

prepared by boiling water for 1 5 

minutes. Subsequently, while maintaining the temperature at 9 0 °C, bubble a 

contaminant-free inert gas through the 

water for one hour. While still hot, 

transfer the water to a narrow mouth 

screw-cap bottle and seal with a 

Teflon-lined septum and cap. 

6.2 Sodium thiosulfateGranular. 

6.3 Trap Materials 

(ACS) 

6.3.1 Coconut charcoal (6/1 0 mesh 

sieved to 26 mesh), (Barnaby Chaney, 

CA-580-2 6 lot tt M 264 9 or 

equivalent). 

6.3.2 2,6-Diphenylene oxide 

polymer—Tenax, (60/8 0 mesh), 

chromatographic grade or equivalent. 

6.3.3 Methyl silicone packing —3 % 

OV-1 on 60/8 0 mesh Chromosorb-W 

or equivalent. 

6.3.4 Silica gel—35/60 mesh, 

Davison, grade-1 5 or equivalent. 

6.4 Methyl Alcohol —Pesticide quality 

or equivalent. 

6.5 Stock standard solutions —Stock 

standard solutions may be prepared 

from pure standard materials or 

purchased as certified solutions. 

Prepare stock standard solutions in 

methyl alcohol using assayed liquids or 

gas cylinders as appropriate. Because 

of the toxicity of some of the 

organohalides, primary dilutions of 

these materials should be prepared in a 

hood. A NIOSH/MESA approved toxic 

gas respirator should be used when the 

analyst handles high concentrations of 

such materials. 

6.5.1 Place about 9.8 mL of methyl 

alcohol into a 1 0-mL ground glass 

stoppered volumetric fiask. Allow the 

flask to stand, unstoppered, for about 

1 0 minutes or until all alcohol wetted 

surfaces have dried. Weigh the fiask to 

the nearest 0.1 mg. 

6.5.2 Add the assayed reference 

material: 

6.5.2.1 Liquids-Using a 100-pL 

syringe, immediately add two or more 

drops of assayed reference material to 

the flask, then reweigh. Be sure that 

the drops fall directly into the alcohol 

without contacting the neck of the 

flask. 

6.5.2.2 Gases —To prepare standards 

for any of the six halocarbons that boil 

below 3 0 °C (bromomethane, chloroethane, chloromethane, dichlorodifluoromethane, trichlorofluoromethane, 

vinyl chloride), fill a 5-mL valved gastight syringe with the reference 

standard to the 5.0-mL mark. Lower 

the needle to 5 mm above the methyl 

alcohol meniscus. Slowly introduce the 

reference standard above the surface 

of the liquid (the heavy gas will rapidly 

dissolve into the methyl alcohol). 

6.5.3 Reweigh, dilute to volume, 

stopper, then mix by inverting the flask 

several times. Calculate the concentration in micrograms per microliter from 

the net gain in weight. When compound 

purity is assayed to be 96 % or greater, 

the weight can be used without correction to calculate the concentration of 

the stock standard. Commercially prepared stock standards can be used at 

any concentration if they are certified 

by the manufacturer or by an independent source. 

6.5.4 Transfer the stock siandard 

solution into a Teflon-sealed screw-cap 

bottle. Store, with minimal headspace, 

at - 1 0 to - 2 0 °C and protect from 

light. 

6.5.5 Prepare fresh standards weekly 

for the six gases and 2-chloroethylvinyl 

ether. All other standards must be 

replaced after one month, or sooner if 

comparison with check standards 

indicate a problem. 

6.6 Secondary dilution standards -

Using stock standard solutions, prepare 

secondary dilution standards in methyl 

alcohol that contain the compounds of 

interest, either singly or mixed together. 

The secondary dilution standards 

should be prepared at concentrations 

such that the aqueous calibration 

standards prepared in Sections 7.3.1 

or 7.4.1 will bracket the working range 

of the analytical system. Secondary 

dilution standards should be stored 

with minimal headspace and should be 

checked frequently for signs of degradation or evaporation, especially just 

prior to preparing calibration standards 

from them. Quality control check 

standards that can be used to 

determine the accuracy of calibration 

standards will be available from the 

U.S.' Environmental Protection Agency, 

Environmental Monitoring and Support 

Laboratory, in Cincinnati, Ohio. 

601-3 July 1982 
P.5 

7. Calibration 

7.1' Assemble a purge and trap device 

that meets the specifications in Section 

5.2. Condition the trap overnight at 

1 80 °C by backflushing with an inert 

gas flow of at least 20 mL/min. Prior to 

use, daily condition traps 1 0 minutes 

while backflushing at 1 80 °C. 

7.2 Connect the purge and trap 

device to a gas chromatograph. The 

gas chromatograph must be operated 

using temperature and flow rate parameters equivalent to those in Table 1. 

Calibrate the purge and trap-gas 

chromatographic system using either 

the external standard technique 

(Section 7.3) or the internal standard 

technique (Section 7.4). 

7.3 External standard calibration 

procedure: 

7.3.1 Prepare calibration standards 

at a minimum of three concentration 

levels for each parameter by carefully 

adding 20.0 pL of one or more secondary dilution standards to 1 00 , 500 , or 

1 00 0 mL of reagent water. A 25-pL 

syringe with a 0.00 6 inch ID needle 

should be used for this operation. One 

of the external standards should be at a 

concentration near, but above, the 

method detection limit (See Table 1) 

and the other concentrations should 

correspond to the expected range of 

concentrations found in real samples or 

should define the working range of the 

detector. These aqueous standards can 

be stored up to 24 hours, if held in 

sealed vials with zero headspace as 

described in Section 9.2. If not so 

stored, they must be discarded after 

one hour. 

7.3.2 Analyze each calibration 

standard according to Section 1 0, and 

tabulate peak height or area responses 

versus the concentration in the 

standard. The results can be used to 

prepare a calibration curve for each 

compound. Alternatively, if the ratio of 

response to concentration (calibration 

factor) is a constant over the working 

range (-=10% relative standard deviation, RSD), linearity through the origin 

can be assumed and the average ratio 

or calibration factor can be used in 

place of a calibration curve. 

7.3.3 The working calibration curve 

or calibration factor must be verified on 

each working day by the measurement 

of one or more calibration standards. If 

the response for any parameter varies 

from the predicted response by more 

than ± 10% , the test must be repeated 

using a fresh calibration standard. 

Alternatively, a new calibration curve 

or calibration factor must be prepared 

for that parameter. 

7.4 Internal standard calibration 

procedure. To use this approach, the 

analyst must select one or more internal 

standards that are similar in analytical 

behavior to the compounds of interest. 

The analyst must further demonstrate 

that the measurement of the internal 

standard is not affected by method or 

matrix interferences. Because of these 

limitations, no internal standard can be 

suggested that is applicable to all 

samples. The compounds recommended 

for use as surrogate spikes in Section 

8.7 have been used successfully as 

internal standards, because of their 

generally unique retention times. 

7.4.1 Prepare calibration standards 

at a minimum of three concentration 

levels for each parameter of interest as 

described in Section 7.3.1 . 

7.4.2 Prepare a spiking solution containing each of the internal standards 

using the procedures described in 

Sections 6.5 and 6.6. It is recommended that the secondary dilution 

standard be prepared at a concentration of 1 5 pg/mL of each internal 

standard compound. The addition of 

1 OpL of this standard to 5.0 mL of 

sample or calibration standard would 

be equivalent to 3 0 pg/L. 

7.4.3 Analyze each calibration standard, according to Section 10, adding 

1 0 p L of internal standard spiking solution directly to the syringe (Section 

10.4). Tabulate peak height or area 

responses against concentration for 

each compound and internal standard, 

and calculate response factors (RF) for 

each compound using equation 1. 

Eq. 1 RF = (AsCis)/(AisCs) 

where: 

As = Response for the parameter to 

be measured. 

AIS = Response for the internal 

standard. 

Cis = Concentration of the internal 

standard. 

Cs = Concentration of the 

parameter to be measured. 

If the RF value over the working range 

is a constant («c1 0 % RSD), the RF can 

be assumed 10 be invariant ar.d the 

average RF can be used for calculations. 

Alternatively, the resuhs can be used 

to plot a calibration curve of response 

ratios, As /Ai s , vs. RF. 

7.4.4 The working calibration curve 

or RF must be verified on each working 

day by the measurement of one or 

more calibration standards. If the 

response for any parameter varies from 

the predicted response by more than 

± 1 0-%, the test must be repeated 

using a fresh calibration standard. 

Alternatively, a new calibration curve 

must be prepared for that compound. 

8. Quality Control 

8.1 Each laboratory that uses this 

method is required to operate a formal 

quality control program. The minimum 

requirements of this program consist of 

an initial demonstration of laboratory 

capability and the analysis of spiked 

samples as a continuing check on 

performance. The laboratory is required 

to maintain performance records to 

define the quality of data that is 

generated. Ongoing performance 

checks must be compared with established performance criteria to determine 

if the results of analyses are within 

accuracy and precision limits expected 

of the method. 

8.1.1 Before performing any 

analyses, the analyst must demonstrate 

the ability to generate acceptable 

accuracy and precision with this 

method. This ability is established as 

described in Section 8.2. 

8.1.2 In recognition of the rapid 

advances that are occurring in chromatography, the analyst is permitted certain options to improve the separations 

or lower the cost of measurements. 

Each time such modifications are made 

to the method, the analyst is required 

to repeat the procedure in Section 8.2. 

8.1.3 The laboratory must spike and 

analyze a minimum of 1 0 % of all 

samples to monitor continuing laboratory performance. This procedure is 

described in Section 8.4. 

8.2 To establish the ability to generate 

acceptable accuracy and precision, the 

analyst must perform the following 

operations. 

8.2.1 Select a representative spike 

concentration for each compound to be 

measured. Using stock standards, 

prepaie a quality control check sample 

concentrate in methyl alcohol 50 0 

times more concentrated than the 

selected concentrations. Quality 

control check sample concentrates, 

appropriate for use with this method, 

will be available from the U.S. 

Environmental Protection Agency, 

Environmental Monitoring and Support 

Laboratory, Cincinnati, Ohio 45268 . 

8.2.2 Using a syringe, add 10 pL of 

the check sample concentrate to each 

of a minimum of four 5-mL aliquots of 

reagent water. A representative waste601-4 July 1982 
P.6 

water may be used in place of the 

reagent w-jater, but one or more additional aliquots must be analyzed to 

determine background levels, and the 

spike level must exceed twice the 

background level for the test to be 

valid. Analyze the aliquots according to 

the method beginning in Section 10. 

8.2.3 Calculate the average percent 

recovery, (R), and the standard deviation of the percent recovery (s), for the 

results. Wastewater background corrections must be made before R and s 

calculations are performed. 

8.2.4 Using Table'2, note the average 

recovery (X) and standard deviation (p) 

expected for each method parameter. 

Compare these to the calculated values 

for R and s. If s > 2p or |X — R| =— 2p, 

review potential problem areas and 

repeat the test. 

8.3 The analyst must calculate 

method performance criteria and define 

the performance of the laboratory for 

each spike concentration and parameter 

being measured. 

8.2.5 The U.S. Environmental 

Protection Agency plans to establish 

performance criteria for R and s based 

upon the results of interlaboratory 

testing. When they become available, 

these criteria must be met before any 

samples may be analyzed. 

8.3.1 Calculate upper and lower 

control limts for method performance: 

Upper Control Limit (UCL) = R + 3s 

Lower Control Limit (LCD = R - 3s 

where R and s are calculated as in 

Section 3.2.3. The UCL and LCL can 

be used to construct control charts171 

that are useful in observing trends in 

performance. The control limits above 

must be replaced by method performance criteria as they become available 

from the U.S. Environmental Protection 

Agency. 

8.3.2 The laboratory must develop 

and maintain separate accuracy statements of laboratory performance for 

wastewater samples. An accuracy 

statement for the method is defined as 

R ± s. The accuracy statement should 

be developed by the analysis of four 

aliquots of wastewater es described in 

Section 8.2.2 , followed by the calculation of R and s. Alternately, the 

analyst may use four wastewater data 

points gathered through the requirement for continuing quality control in 

Section 8.4. The accuracy statements 

should be updated regularly.'7' 

8.4 The laboratory is required to 

collect a portion of their samples in 

duplicate to monitor spike recoveries. 

The frequency of spiked sample 

analysis must be at least 1 0 % of all 

samples or one sample per month, 

whichever is greater. One aliquot of the 

sample must be spiked and analyzed as 

described in Section 8.2. If the 

recovery for a particular parameter 

does not fall within the control limits 

for method performance, the results 

reported for that parameter in all 

samples processed as part of the same 

set must be qualified as described in 

Section 11.3 . The laboratory should 

monitor the frequency of data so 

qualified to ensure that it remains at or 

below 5%. 

8.5 Each day, the analyst must 

demonstrate through the analysis of 

reagent water, that interferences from 

the analytical system are under control. 

8.6 It is recommended that the 

laboratory adopt additional quality 

assurance practices for use with this 

method. The specific practices that are 

most productive depend upon the 

needs of the laboratory and the nature 

of the samples. Field duplicates may be 

analyzed to monitor the precision of 

the sampling technique. When doubt 

exists over the identification of a peak 

on the chromatogram, confirmatory 

techniques such as gas chromatography 

with a dissimilar column, specific 

element detector, or mass spectrometer must be used. Whenever possible, 

the laboratory should perform analysis 

of standard reference materials and 

participate in relevant performance 

evaluation studies. 

8.7 The analyst should maintain 

constant surveillance of both the performance of the analytical system and 

the effectiveness of the method in 

dealing with each sample matrix by 

spiking each sample, standard and 

blank with surrogate halocarbons. A 

combination of bromochloromethane, 

2-bromo-1-chloropropane, and 

1,4-dichlorobutane is recommended to 

encompass the range of the temperature program used in this method. From 

stock standard solutions prepared as 

above, add a volume to give 750 0 p g 

of each surrogate to 4 5 mL of reagent 

water contained in a 50-mL volumetric 

flask, mix and dilute to volume (1 5 

ng/pL). If the internal standard calibration proceduie is being used, the 

surrogate compounds may be added 

directly to the internal standard spiking 

solution (Section 7.4.2). Add 1 Op L of 

this surrogate spiking solution directly 

into the 5-mL syringe with every sample 

and reference standard analyzed. 

Prepare a fresh surrogate spiking 

solution on a weekly basis. 

9. Sample Collection, 

Preservation, and Handling 

9.1 All samples must be iced or 

refrigerated from the time of collection 

until extraction. If the sample contains 

free or combined chlorine, add sodium 

thiosulfate preservative (10 mg/40 mL 

is sufficient for up to 5 ppm Clj) to the 

empty sample bottle just prior to 

shipping to the sampling site. USEPA 

methods 330. 4 and 330. 5 may be 

used for measurement of residual 

chlorine.18' Field test kits are available 

for this purpose. 

9.2 Grab samples must be collected 

in glass containers having a total 

volume of at least 25 mL. Fill the 

sample bottle just to overflowing in 

such a manner that no air bubbles pass 

through the sample as the bottle is 

being filled. Seal the bottle so that no 

air bubbles are entrapped in it. If 

preservative has been added, shake 

vigorously for one minute. Maintain the 

hermetic seal on the sample bottle until 

time of analysis. 

9.3 All samples must be analyzed 

within 14 days of collection. 

10. Sample Extraction and 

Gas Chromatography 

10.1 Table 1 summarizes the 

recommended operating conditions for 

the gas chromatograph. Included in this 

Table are estimated retention times and 

method detection limits that can be 

achieved by this method. An example 

of the separations achieved by Column 

1 is shown in Figure 5. Other packed 

columns, chromatographic conditions, 

or detectors may be used if the 

requirements of Section 8.2 are met. 

10.2 Calibrate the system daily as 

described in Section 7. 

10.3 Adjust the purge gas (nitrogen 

or helium) flow rate to 4 0 mL/min. 

Attach the trap inlet to the purging 

device, and set the device to purge. 

Open the syringe valve located on the 

purging device sample introduction 

needle. 

10.4 Allow sample to come to 

ambient temperature prior lo introducing it to the syringe. Remove the 

plunger from a 5-mL syringe and attach 

a closed syringe valve. Open the sample 

bottle (or standard) and carefully pour 

the sample into the syringe barrel to 

just short of overflowing. Replace the 

601-5 July 1982 
P.7 

syringe plunger and compress the 

sample. Q.pen the syringe valve and 

vent any residual air while adjusting the 

'sample volume to 5.0 mL. Since this 

process of taking an aliquot destroys 

the validity of the sample for future 

analysis, the analyst should fill a 

second syringe at this time to protect 

against possible loss of data. Add 

1 0.0 pL of the surrogate spiking solution (8.7) and 1 0.0 pL of the internal 

standard spiking solution (Section 

7.4.2), if applicable, through the valve 

bore, then close the valve. 

10.5 Attach the syringe-syringe 

valve assembly to the syringe valve on 

the purging device. Open the syringe 

valves and inject the sample into the 

purging chamber. 

10.6 Close both valves and purge the 

sample for 1 1.0 ± .1 minutes at 

ambient temperature. 

10.7 After the 1 1 -minute purge time, 

attach the trap to the chromatograph, 

adjust the device to the desorb mode, 

and begin to temperature program the 

gas chromatograph. Introduce the 

trapped materials to the GC column by 

rapidly heating the trap to 1 8 0 °C 

while backflushing the trap with an 

inert gas between 2 0 and 6 0 mL/min 

for four minutes. If rapid heating of the 

trap cannot be achieved, the gas 

chromatographic column must be used 

as a secondary trap by cooling it to 

3 0 °C (subambient temperature, if poor 

peak geometry or random retention 

time problems persist) instead of the 

initial program temperature of 4 5 °C. 

10.8 While the trap is being desorbed 

into the gas chromatograph, empty the 

purging chamber using the sample introduction syringe. Wash the chamber 

with two 5-mL flushes of reagent 

water. 

10.9 After desorbing the sample for 

four minutes recondition the trap by 

returning the purge and trap device to 

the purge mode. Wait 1 5 seconds then 

close the syringe valve on the purging 

device to begin g3S flow through the 

trap. The trap temperature should be 

maintained at 1 8 0 °C. After approximately seven minutes turn off the trap 

heater and open the syringe valve to 

stop the gas flow through the trap. 

When cool the trap is ready for the 

next sample. 

10.1 0 The width of the retention 

time window used to make identifications should be based upon measurements of actual retention time variations 

of standards over the course of a day. 

Three times the standard deviation of a 

retention time for a compound can be 

used to calculate a suggested window 

size; however, the experience of the 

analyst should weigh heavily in the 

interpretation of chromatograms. 

10.11 If the response for the peak 

exceeds the working range of the 

system, prepare a dilution of the 

sample with reagent water from the 

aliquot in the second syringe and 

reanalyze. 

1 1. Calculations 

11.1 Determine the concentration of 

individual compounds in the sample. 

11.1.1 If the external standard 

calibration procedure is used, calculate 

the concentration of material from the 

peek response using the calibration 

curve or calibration factor determined 

in Section 7.3.2. 

11.1.2 If the internal standard 

calibration procedure was used, calculate the concentration in the sample 

using the response factor (RF) determined in Section 7.4.3 and equation 2. 

Eq. 2. 

Concentration pg/L = (AsCis)/(Ais)(RF) 

where: 

As = Response for the parameter to 

be measured. 

A1S = Response for the internal 

standard. 

Cs = Concentration of the internal 

standard. 

11.2 Report results in micrograms 

per liter. When duplicate and spiked 

samples are analyzed, report all data 

obtained with the sample results. 

11.3 For samples processed as part 

of a set where the spiked sample 

recovery falls outside of the control 

limits which were established according 

to Section 8.3, data for the affected 

parameters must be labeled as suspect. 

12. Method Performance 

12.1 The method detection limit 

(MDL) is defined as the minimum 

concentration of a substance that can 

be measured and reported with 99 % 

confidence that the value is above 

zero.11' The MDL concentrations listed 

in Table 1 were obtained using reagent 

water.19' Similar results were achieved 

using representative wastewaters. The 

MDL actually achieved in a given 

analysis will vary depending on instrument sensitivity and matrix effects. 

1 2.2 This method is recommended 

for use in the concentration range from 

the MDL up to 1 00 0 x MDL. Direct 

aqueous injection techniques Should be 

used to measure concentration levels 

above 100 0 x MDL. 

12.3 In a single laboratory (Monsanto 

Research), using reagent water and 

• wastewaters spiked at or near background levels, the average recoveries 

presented in Table 2 were obtained19'. 

The standard deviation of the measurement in percent recovery is also 

included in Table 2<9'. 

12.4 The U.S. Environmental 

Protection Agency is in the process of 

conducting an interlaboratory method 

study to fully define the performance 

of this method. 

References 

1. See Appendix A. 

2. Bellar, T.A., and Lichtenberg, J.J. 

Journal American Water Works 

Association, 66, 739 , (1974). 

3. Bellar, T.A., and Lichtenberg, J.J. 

"Semi-Automated Headspace Analysis 

of Drinking Waters and Industrial 

Waters for Purgeable Volatile Organic 

Compounds," Proceedings from 

Symposium on Measurement of 

Organic Pollutants in Water and 

Wastewater, American Society for 

Testing and Materials, STP 686 , CE . 

Van Hall, editor, 1978 . 

4. "Carcinogens —Working With 

Carcinogens," Department of Health, 

Education, and Welfare, Public Health 

Service, Center for Disease Control, 

National Institute for Occupational . 

Safety and Health, Publication No. 

77-206 , Aug. 1977 . 

5. "OSHA Safety and Health Standards, General Industry," (29 CFR 

1910), Occupational Safety and 

Health Administration, OSHA 2206 , 

(Revised, January, 1976). 

6. "Safety in Academic Chemistry 

Laboratories," American Chemical 

Society Publication, Committee on 

Chemical Safety, 3rd Edition, 1 979 . 

7. "Handbook for Analytical Quality 

Control in Water and Wastewater 

Laboratories," EPA-600/4-79-01 9, 

U.S. Environmental Protection Agency, 

Environmental Monitoring and Support 

Laboratory —Cincinnati, Ohio 45268 , 

March 1979 . 

8. "Methods 330. 4 (Titrimetric, DPDFAS) and 330. 5 (Spectrophotometric, 

DPD) for Chlorine, Total Residual," 

Methods for Chemical Analysis of Water 

and Wastes, EPA 600/4-79-020 , U.S. 

Environmental Protection Agency, 

601-6 July 1982 
P.8 

Environmental Monitoring and Support 

Laboratory —Cincinnati, Ohio 45268, 

March'l,9'79. 

'9. "EPA Method Validation Study 23, 

Method 601 (Purgeable Halocarbons)," 

Report for EPA Contract 68-03-2856 

(In preparation). 

Table 1. Chromatographic Conditions and Method Detection Limits 

Parameter 

Chloromethane 

Bromomethane 

Dichlorodifluoromethane 

Vinyl chloride 

Chloroethane 

Methylene chloride 

Trichlorofluoromethane 

1,1 -Dichloroethene 

1,1 -Dichloroethane 

trans-1,2-Dichloroethene 

Chloroform 

1,2-Dichloroethane 

1,1,1 -Trichloroethane 

Carbon tetrachloride 

Bromodichloromethane 

1,2-Dichloropropane 

trans-1,3-Dichloropropene 

Trichloroethene 

Dibromochloromethane 

1,1,2-Trichloroethane 

cis-1,3-Dichloropropene 

2-Chloroethylvinyl ether 

Bromoform 

1, 1,2,2-Tetrachloroethane 

Tetrachloroethene 

Chlorobenzene 

1,3-Dichloroben/ene 

1,2-Dichlorobenzene 

1,4-Dichlorobenzene 

Retention Time 

Column 1 

1.50 

2.17 

2.62 

2.67 

3.33 

5.25 

7.18 

7.93 

9.30 

10.1 

10.7 

11.4 

12.6 

13.0 

13.7 

14.9 

15.2 

15.8 

16.5 

16.5 

16.5 

18.0 

19.2 

21.6 

21.7 

24.2 

34.0 

34.9 

35.4 

(mm.) 

Column 2 

5.28 

7.05 

nd 

5.28 

8.68 

10.1 

nd 

7.72 

12.6 

9.38 

12.1 

15.4 

13.1 

14.4 

14.6 

16.6 

16.6 

13.1 

16.6 

18.1 

18.0 

nd 

19.2 

nd 

15.0 

18.8 

22.4 

23.5 

22.3 

Method 

Detection Limit 

M/L 

0.08 

1.18 

1.81 

0.18 

0.52 

0.25 

nd 

0. 13 

0.07 

0.10 

0.05 

0.03 

0.03 

0.12 

0.10 

0.04 

0.34 

0.12 

0.09 

0.02 

0.20 

0. 13 

0.20 

0.03 

0.03 

0.25 

0.32 

0.15 

0.24 

nd = not determined 

Column 1 conditions: Carbopack B 60/80 mesh coated with 1 % SP-1000 packed in 

an 8 ft x 0.1 in ID stainless steel or glass column with helium carrier gas at 40 

mL/min flowrate. Column temperature held at 45° C for 3 min. then programmed 

at 8 °C/min. to 220 ° and held for 15 min. 

Column 2 conditions: Porasil-C 100/120 mesh coated with n-octane packed in a 6 ft 

x 0.1 in ID stainless steel or glass column with helium carrier gas at 40 mL/min 

flow rate. Column temperature held at 50°C for 3 min then programmed at 

6°C/min to 170° and held for 4 min. -

601-7 July 1982 
P.9 

Table 2. Single Operator Accuracy and Precision 

' • * 

. ' 

Parameter 

Br oinodichlorome thane 

Bromoform 

Bromomethane 

Carbon tetrachloride 

Chlorobenzene 

Chloroethane 

2-Chloroethylvinyl ether 

Chloioform 

Chloromethane 

Dibrornochlcromethane 

1,2-Dichlorobenzene. 

1,3-Dichlorobenzene' 

1,4-Dichlorobenzene 

Dichlorodifluorome thane 

1, 1-Dich/orcethane 

1,2-Dichloroethane 

1, 1 -Dichloroethene 

trans-1,2-Dichloroethene 

1,2-Dichloropropane 

cis-1,3-Dichloropropene 

trans-1,3-Dichloropropene 

Methylene chloride 

1,1,2,2-Tetrachloroethane 

Tetrachloroethene 

1, 1,1-Trichloroethane 

1, 1,2-Trichloroethane 

Trichloroethene 

Trichlorofluoromethane 

Vinyl chloride 

A verage 

Percent 

Recovery 

100.9 

89.5 

105.0 

82.5 

93.9 

91.5 

96.3 

101.7 

91.4 

98.3 

10.20 

91.6 

9 7.5 

87.8 

102.3 

9 7.8 

101.1 

91.0 

97.7 

86.7 

73.5 

97.9 

91.9 

94.1 

75.1 

91.0 

106.1 

89.3 

101.9 

Standard 

Deviation 

% 

5.0 

9.0 

17.3 

25.6 

8.9 

22.4 

9.9 

20.6 

13.4 

6.5 

2.0 

4.3 

9.3 

18.0 

5.5 

4.8 

21.7 

19.3 

8.8 

6.0 

17.2 

2.6 

15.0 

18.1 

12.5 

25.1 

7.4 

13.9 

11.4 

Spike 

Range 

(ug/U 

0.43-46.7 

1.45-50 

3.39-49.2 

0.55-50 

2.21-50 

3.95-50 

4.39-133 

0.44-50 

0.55-23.9 

0.75-93.0 

4.89-154 

2.94-46.7 

2.99-51.6 

2. 18-43.4 

0.44-46.7 

0.44-46.7 

0.37-50 

0.44-98.0 

0.29-39.0 

0.44-46.7 

0.43-50 

0. 73-46. 7 

0.46-46.7 

0.50-35.0 

0.37-29.0 

0.45-50 

0.38-46.7 

149 

0.82-32.3 

Number 

of 

Analyses 

21 

20 

21 

19 

20 

21 

20 

20 

21 

21 

21 

21 

21 

21 

21 

21 

19 

20 

21 

21 

20 

21 

21 

21 

21 

21 

21 

14 

21 

Optional 

Foam 

Trap 

Matrix 

Types 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

3 

2 

3 

( ^ 

^ 

_Exit V 4 in. 

O.D. 

-*. 14mm 

O.D. 

Inlet V 4 in. 

O.D. 

V 4 in. 

O.D. exit 

Sample Inlet 

2-way Syringe valve 

^"— 17cm 20 gauge syringe needle 

1

 6mm O.D. Rubber Septum 

^10mm O.D. '/, „ in. O.D. 

— /Stainless Steel - Inlet 

/« in. O.D. 

13X molecular 

/

,/A sieve purge 

gas filter 

Purge gas 

flow control 

10mm glass frit 

medium porosity 

601-8 

Figure 1 . Purging device 

July 1982 
P.10 

Packing procedure Construction 

Glass 5mm f ^ 

wool 

Activated 7.7cm yz 

charcoal 

Grade 15 

Silica gel 7.7cm 

Tenax 7.7cm 

3% OV-1 

Glass 

wool 

1 cm 

5mm 

7

n

i'foot 

resistance 

wire wrapped 

solid 

(Double layer) 

15 cm 

Tv'foot 

resistance 

wire wrapped 

solid 

(Single layer) 

8cm — 

Compression fitting 

nut and ferrules 

Thermocouple/ 

controller 

sensor 

Electronic 

temperature 

control 

end 

pyrometer 

Tubing 25 cm. 

0.105 in. ID. 

0.125 in O.D. 

stainless steel 

Trap inlet 

Figure 2. Trap packings and construction to include desorb capability 

Carrier gas flow control 

Pressure regulator \y^—fe^dPurge gas 

flow control \ 

13X molecular 

sieve filter 

Liquid injection ports 

Column oven 

~"ir~fc>l—i M i IJ u "

 >C— Confirmatory column 

^ L -Analytical column 

\ optional 4-port column 

6-port selection valve 

valve / TraP

 in,et 

Resistance wire 

^yHeater control 

Purging 

device 

Note: 

All lines between 

trap and GC 

should be heated 

to 80°C 

Figure 3. Schematic of purge and trap device — purge mode 

601-9 July 1982 
P.11 

Carrier gas flow control 

yl' a 

Pressure regulator 

Purge gas v 

flow control v | 

Liquid injection ports r , ^ . ' H ^.Column oven 

^..JWbl!-, n H f l H—^ — Confirmatory column 

CM '^j ,. n n n._L>

 r°detector 

iQipj^UU1

 t 

73X molecular 

sieve filter 

Analytical column 

ional 4-port column 

selection valve 

Trap inlet 

Resistance wire 

! On 

.Heater control 

Purging 

de vice 

Note: 

All lines between 

trap and GC 

should be heated 

to 80°C 

Figure 4 . Schematic of purge and trap device — desorb mode 

Column: 1% SP-1000 on Carbopack-8 

Program: 45°C-3 minutes. 8°/minute to 220°C 

Del act or; Hall 700-A electrolytic conductivity 

Retention time, minutes 

Figure 5. Gas chromatogram of purgeable halocarbons 

601-10 July 1982