EPA Methods List with Links

   Method 313A - Determination Of Residual Hydrocarbons In Rubber Crumb 

1.0 Scope and Application

1.1 This method determines residual toluene and styrene in stripper crumb of the of the following types of rubber: polybutadiene (PBR) and styrene/butadiene rubber (SBR), both derived from solution polymerization processes that utilize toluene as the polymerization solvent.
1.2 The method is applicable to a wide range of concentrations of toluene and styrene provided that calibration standards cover the desired range. It is applicable at least over the range of 0.01 to 10.0 % residual toluene and from 0.1 to 3.0 % residual styrene. It is probably applicable over a wider range, but this must be verified prior to use.
1.3 The method may also be applicable to other process samples as long as they are of a similar composition to stripper crumb. See section 3.1 of this method for a description of stripper crumb.
2.0 Summary of Method
2.1 The wet crumb is placed in a sealed vial and run on a headspace sampler which heats the vial to a specified temperature for a specific time and then injects a known volume of vapor into a capillary GC. The concentration of each component in the vapor is proportional to the level of that component in the crumb sample and does not depend on water content of the crumb.
2.2 Identification of each component is performed by comparing the retention times to those of known standards.

2.3 Results are calculated by the external standard method since injections are all performed in an identical manner.

The response for each component is compared with that obtained from dosed samples of crumb.
2.4 Measured results of each compound are corrected by dividing each by the average recovery efficiency determined for the same compound in the same sample type.

3.0 Definitions
3.1 Stripper crumb refers to pieces of rubber resulting from the steam stripping of a toluene solution of the same polymer in a water slurry. The primary component of this will be polymer with lesser amounts of entrained water and residual toluene and other hydrocarbons. The amounts of hydrocarbons present must be such that the crumb is a solid material, generally less that 10 % of the dry rubber weight. 4.0 Interferences
4.1 Contamination is not normally a problem since samples are sealed into vials immediately on sampling.
4.2 Cross contamination in the headspace sampler should not be a problem if the correct sampler settings are used. This should be verified by running a blank sample immediately following a normal or high sample. Settings may be modified if necessary if this proves to be a problem, or a blank sample may be inserted between samples.
4.3 Interferences may occur if volatile hydrocarbons are present which have retention times close to that of the components of interest. Since the solvent makeup of the processes involved are normally fairly well defined this should not be a problem. If it is found to be the case, switching to a different chromatographic column will probably resolve the situation.
5.0 Safety
5.1 The chemicals specified in this method should all be handled according to standard laboratory practices as well as any special precautions that may be listed in the MSDS for that compound.

5.2 Sampling of strippers or other process streams may involve high pressures and temperatures or may have the potential for exposure to chemical fumes. Only personnel who have been trained in the specific sampling procedures required for that process should perform this operation. An understanding of the process involved is necessary. Proper personal protective equipment should be worn. Any sampling devices should be inspected prior to use. A detailed sampling procedure which specifies exactly how to obtain the sample must be written and followed.

6.0 Equipment and Supplies
6.1 Hewlett Packard (HP) 7694 Headspace sampler, or equivalent, with the following conditions:

       Times (min.):  GC cycle time 6.0 , vial equilibration               30.0 , pressurization 0.25 , loop fill 0.25,               loop equilibration 0.05 , inject 0.25 
       Temperatures (deg C):  oven 70, loop 80, transfer               line 90 
       Pressurization gas:  He @ 16 psi 

6.2 HP 5890 Series II capillary gas chromatograph, or equivalent, with the following conditions:

Column: Supelco SPB-1, or equivalent, 15m x .25mm x .25F film
Carrier: He @ 6 psi
Run time: 4 minutes

Oven: 70 deg C isothermal Injector: 200 deg C split ratio 50:1 Detector: FID @ 220 deg C

6.3 HP Chemstation consisting of computer, printer and Chemstation software, or an Page 3

equivalent chromatographic data system.
6.4 20 ml headspace vials with caps and septa.
6.5 Headspace vial crimper.
6.6 Microliter pipetting syringes.
6.7 Drying oven at 100 deg C vented into cold trap or other means of trapping hydrocarbons released.
6.8 Laboratory shaker or tumbler suitable for the headspace vials.
6.9 Personal protective equipment required for sampling the process such as rubber gloves and face and eye protection.
7.0 Reagents and Standards
7.1 Toluene, 99.9+% purity, HPLC grade.
7.2 Styrene, 99.9+% purity, HPLC grade.
7.3 Dry rubber of same type as the stripper crumb samples.
8.0 Sample Collection, Preservation and Storage
8.1 Collect a sample of crumb in a manner appropriate for the process equipment being sampled.
8.1.1 If conditions permit, this may be done by passing a stream of the crumb slurry through a strainer, thus separating the crumb from the water. Allow the water to drain freely, do not attempt to squeeze any water from the crumb. Results will not depend on the exact water content of the samples. Immediately place several pieces of crumb directly into a headspace vial. This should be done with rubber gloves to protect the hands from both the heat and from contact with residual hydrocarbons. The vial should be between 1/4 and 1/3 full. Results do not depend on sample size as long as there is sufficient sample to reach an equilibrium vapor pressure in the headspace of the vial. Cap and seal the vial. Prepare each sample at least in duplicate. This is to minimize the effect of the variation that naturally occurs in the composition of non homogeneous crumb. The free water is not analyzed by this method and should be disposed of appropriately along with any unused rubber crumb.
8.1.2 Alternatively the process can be sampled in a specially constructed sealed bomb which can then be transported to the laboratory. The bomb is then cooled to ambient temperature by applying a stream of running water. The bomb can then be opened and the

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crumb separated from the water and the vials filled as described in section 8.1.1 of this method. The bomb may be stored up to 8 hours prior to transferring the crumb into vials. 8.2 The sealed headspace vials may be run immediately or may be stored up to 72 hours prior to running. It is possible that even longer storage times may be acceptable, but this must be verified for the particular type of sample being analyzed (see section 9.2.3 of this method). The main concern here is that some types of rubber eventually may flow, thus compacting the crumb so that the surface area is reduced. This may have some effect on the headspace equilibration.

9.0 Quality Control
9.1 The laboratory is required to operate a formal quality control program. This consists of an initial demonstration of the capability of the method as well as ongoing analysis of standards, blanks and spiked samples to demonstrate continued performance.
9.1.1 When the method is first set up a calibration is run (described in section 10 of this method) and an initial demonstration of method capability is performed (described in section 9.2 of this method). Also recovery efficiency for each type of sample must be determined (see section 9.4 of this method).

9.1.2 It is permissible to modify this method in order to improve separations or make other improvements, provided that all performance specifications are met. Each time a modification to the method is made it is necessary to repeat the calibration (section 10 of this method), the demonstration of method performance (section 9.2 of this method) and the recovery efficiency for each type of sample (section 9.4 of this method).

9.1.3 Ongoing performance should be monitored by running a spiked rubber standard. If this test fails to demonstrate that the analysis is in control, then corrective action must be taken. This method is described in section 9.3 of this method.
9.1.4 If new types of samples are being analyzed then recovery efficiency for each new type of sample must be determined. New type includes any change, such as polymer type, physical form or a significant change in the composition of the matrix.

9.2 Initial demonstration of method capability to establish the accuracy and precision of the method. This is to be run following the calibration described in section 10 of this method.

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9.2.1 Prepare a series of identical spiked rubber standards as described in section 9.3 of this method. A sufficient number to determine statistical information on the test should be run. Ten may be a suitable number, depending on the quality control methodology used at the laboratory running the tests. These are run in the same manner as unknown samples (see section 11 of this method).

9.2.2 Determine mean and standard deviation for the results. Use these to determine the capability of the method and to calculate suitable control limits for the ongoing performance check which will utilize the same standards.
9.2.3 Prepare several additional spiked rubber standards and run 2 each day to determine the suitability of storage of the samples for 24, 48 and 72 hours or longer if longer storage times are desired.

9.3 A spiked rubber standard should be run on a regular basis to verify system performance. This would probably be done daily if samples are run daily. This is prepared in the same manner as the calibration standards (section 10.1 of this method), except that only one concentration of toluene and styrene is prepared. Choose concentrations of toluene and styrene that fall in the middle of the range expected in the stripper crumb and then do not change these unless there is a major change in the composition of the unknowns. If it becomes necessary to change the composition of this standard the initial performance demonstration must be repeated with the new standard (section 9.2 of this method).
9.3.1 Each day prepare one spiked rubber standard to be run the following day. The dry rubber may be prepared in bulk and stored for any length of time consistent with the shelf life of the product. The addition of water and hydrocarbons must be performed daily and all the steps described under section 10.1 of this method must be followed.
9.3.2 Run the spiked rubber standard prepared the previous day. Record the results and plot on an appropriate control chart or other means of determining statistical control. 9.3.3 If the results for the standard indicate that the test is out of control then corrective action must be taken. This may include a check on procedures, instrument settings, maintenance or recalibration. Samples may be stored (see section 8.2 of this method) until compliance is demonstrated.
9.4 Recovery efficiency must be determined once for each sample type and whenever

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modifications are made to the method.
9.4.1 For each sample type collect 12 samples from the process (section 8.1 of this method). This should be done when the process is operating in a normal manner and residual hydrocarbon levels are in the normal range. Half the vials and caps should be tared, labeled “spiked” and numbered 1 through 6. The other vials are labeled “unspiked” and need not be tared but are also numbered 1 through 6. Immediately on sampling, the vials should be capped to prevent loss of volatiles. Allow all the samples to cool completely to ambient temperature. Reweigh each of the vials labeled “spiked” to determine the weight of wet crumb inside.
9.4.2 The dry weight of rubber present in the wet crumb is estimated by multiplying the weight of wet crumb by the fraction of nonvolatiles typical for the sample. If this is not known, an additional quantity of crumb may be sampled, weighed, dried in an oven and reweighed to determine the fraction of volatiles and nonvolatiles prior to starting this procedure.
9.4.3 To the vials labeled “spiked” add an amount of a mixture of toluene and styrene that is between 40 and 60 % of the amount expected in the crumb. This is done by removing the cap, adding the mixture by syringe, touching the tip of the needle to the sample in order to remove the drop and then immediately recapping the vials. The mixture is not added through the septum, because a punctured septum may leak and vent vapors as the vial is heated. The weights of toluene and styrene added may be calculated from the volumes of the mixture added, its composition and density, or may be determined by the weight of the vials and caps prior to and after addition. The exact dry weight of rubber present and the concentration of residual toluene and styrene are not known at this time so an exact calculation of the concentration of hydrocarbons is not possible until the test is completed.
9.4.4 Place all the vials onto a shaker or tumbler for 24 ± 2 hours. This is essential in order for the hydrocarbons to be evenly distributed and completely absorbed into the rubber. If this is not followed the toluene and styrene will be mostly at the surface of the rubber and high results will be obtained.
9.4.5 Remove the vials from the shaker and tap them so that all the crumb settles to the bottom of the vials. Allow them to stand for 1 hour prior to analysis to allow any liquid to

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drain fully to the bottom.
9.4.6 Run the spiked and unspiked samples in the normal manner. Record the concentrations of toluene and styrene reported for each pair of spiked and unspiked samples with the same vial number.
9.4.7 Open each of the vials labeled “spiked”, remove all the rubber crumb and place it into a tarred drying pan. Place in a 100 deg C oven for two hours, cool and reweigh. Subtract the weight of the tare to give the dry weight of rubber in each spiked vial. Calculate the concentration of toluene and styrene spiked into each vial as percent of dry rubber weight. This will be slightly different for each vial since the weights of dry rubber will be different.
9.4.8 For each hydrocarbon calculate the average recovery efficiency (R) using the following equations:


R =_E(Rn)/6 (average of the 6 individual Rn values) Rn = (Cns - Cnu) / Sn

where: n = vial number
Cns = concentration of compound measured in spiked sample number n. Cnu = concentration of compound measured in unspiked sample number n.

Sn = theoretical concentration of compound spiked into sample n calculated in step 9.4.7

9.4.9 A different R value should be obtained for each compound (styrene and toluene) and for each sample type.
9.4.10 A value of R between 0.70 and 1.30 is acceptable.
9.4.11 R is used to correct all reported results for each compound by dividing the measured results of each compound by the R for that compound for the same sample type (see section 12.2 of this method.)

10.0 Calibration
10.1 Calibration standards are prepared by dosing known amounts of the hydrocarbons of interest into vials containing known amounts of rubber and water.

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10.1.1 Cut a sufficient quantity of dry rubber of the same type as will be analyzed into pieces about the same size as that of the crumb. Place these in a single layer on a piece of aluminum foil or other suitable surface and place into a forced air oven at 100 C for four hours. This is to remove any residual hydrocarbons that may be present. This step may be performed in advance.

10.1.2 Into each of a series of vials add 3.0 g of the dry rubber.
10.1.3 Into each vial add 1.0 ml distilled water or an amount that is close to the amount that will be present in the unknowns. The exact amount of water present does not have much effect on the analysis, but it is necessary to have a saturated environment. The water will also aid in the uniform distribution of the spiked hydrocarbons over the surface of the rubber after the vials are placed on the shaker (in step 10.1.5 of this method).
10.1.4 Into each vial add varying amounts of toluene and styrene by microliter syringe and cap the vials immediately to prevent loss. The tip of the needle should be carefully touched to the rubber in order to transfer the last drop to the rubber. Toluene and styrene may first be mixed together in suitable proportions and added together if desired. The weights of toluene and styrene added may be calculated from the volumes of the mixture added, its composition and density, or may be determined by the weight of the vials and caps prior to and after addition. Concentrations of added hydrocarbons are calculated as percent of the dry rubber weight. At least 5 standards should be prepared with the amounts of hydrocarbons added being calculated to cover the entire range possible in the unknowns. Retain two samples with no added hydrocarbons as blanks.
10.1.5 Place all the vials onto a shaker or tumbler for 24 ± 2 hours. This is essential in order for the hydrocarbons to be evenly distributed and completely absorbed into the rubber. If this is not followed the toluene and styrene will be mostly at the surface of the rubber and high results will be obtained.
10.1.6 Remove the vials from the shaker and tap them so that all the crumb settles to the bottom of the vials. Allow them to stand for 1 hour prior to analysis to allow any liquid to drain fully to the bottom.
10.2 Run the standards and blanks in the same manner as described for unknowns (section 11 of this method), starting with a blank, then in order of increasing hydrocarbon content and ending with the other blank.

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10.3 Verify that the blanks are sufficiently free from toluene and styrene or any interfering hydrocarbons.
10.3.1 It is possible that trace levels may be present even in dry product. If levels are high enough that they will interfere with the calibration then the drying procedure in section 10.1.1 of this method should be reviewed and modified as needed to ensure that suitable standards can be prepared .

10.3.2 It is possible that the final blank is contaminated by the previous standard. If this is the case review and modify the sampler parameters as needed to eliminate this problem. If necessary it is possible to run blank samples between regular samples in order to reduce this problem, though it should not be necessary if the sampler is properly set up.

10.4 Enter the amounts of toluene and styrene added to each of the samples (as calculated in section 10.1.4 of this method) into the calibration table and perform a calibration utilizing the external standard method of analysis.
10.5 At low concentrations the calibration should be close to linear. If a wide range of levels are to be determined it may be desirable to apply a nonlinear calibration to get the best fit.

11.0 Procedure
11.1 Place the vials in the tray of the headspace sampler. Enter the starting and ending positions through the console of the sampler. For unknown samples each is run in duplicate to minimize the effect of variations in crumb composition. If excessive variation is noted it may be desirable to run more than two of each sample.
11.2 Make sure the correct method is loaded on the Chemstation. Turn on the gas flows and light the FID flame.
11.3 Start the sequence on the Chemstation. Press the START button on the headspace unit. The samples will be automatically injected after equilibrating for 30 minutes in the oven. As each sample is completed the Chemstation will calculate and print out the results as percent toluene and styrene in the crumb based on the dry weight of rubber.
12.0 Data Analysis and Calculations
12.1 For each set of duplicate samples calculate the average of the measured concentration of toluene and styrene. If more than two replicates of each sample are run calculate the average over all replicates.

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12.2 For each sample correct the measured amounts of toluene and styrene using the following equation:

Corrected Result = Cm / R
where: Cm = Average measured concentration for that compound.

R = Recovery efficiency for that compound in the same sample type (see section 9.4 of this method)

12.3 Report the recovery efficiency (R) and the corrected results of toluene and styrene for each sample.
13.0 Method Performance
13.1 This method can be very sensitive and reproducible. The actual performance depends largely on the exact nature of the samples being analyzed. Actual performance must be determined by each laboratory for each sample type.

13.2 The main source of variation is the actual variation in the composition of non homogeneous crumb in a stripping system and the small sample sizes employed here. It therefore is the responsibility of each laboratory to determine the optimum number of replicates of each sample required to obtain accurate results.

14.0 Pollution Prevention
14.1 Samples should be kept sealed when possible in order to prevent evaporation of hydrocarbons.
14.2 When drying of samples is required it should be done in an oven which vents into a suitable device that can trap the hydrocarbons released.

14.3 Dispose of samples as described in section 15.
15.0 Waste Management
15.1 Excess stripper crumb and water as well as the contents of the used sample vials should be properly disposed of in accordance with local and federal regulations.
15.2 Preferably this will be accomplished by having a system of returning unused and spent samples to the process.
16.0 References

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16.1 “HP 7694 Headspace Sampler - Operating and Service Manual”, Hewlett-Packard Company, publication number G1290-90310, June 1993

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