Restek Column

Guide to Preparing and Analyzing Semivolatile Organic Compounds
Inside:
Introduction ..................... pg. 2 Extraction Liquid samples ................. pg. 2 Soil samples ..................... pg. 4 Cleanup ............................ pg. 5 Gel Permeation Chromatography .............. pg. 5 Analysis Calibration standards ...... pg. 6 Injection port configuration ................... pg. 6 Column selection ............. pg. 9 Reducing Discrimination ............... pg. 15 Quantitation ................... pg. 16 Summary ........................ pg. 16 Product Listing ........ pg. 1727
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Introduction
This technical guide addresses the preparation and gas chromatographic (GC) analysis of semivolatile organic compounds such as those listed in US Environmental Protection Agency (EPA) Methods 8270, 525, and 625; and polycyclic aromatic hydrocarbons (PAHs) such as those listed in US EPA Methods 610 and 8100. These analyses are some of the most common tests performed by environmental laboratories, yet there are many analytical challenges of which the analyst needs to be aware. For example, the samples often are highly contaminated with non-target compounds (e.g., hydrocarbons) and quality assurance/control (QA/QC) of the methods is rigorous. There are several procedures and techniques that can be employed, however, to make these analyses simpler to perform. Review this guide to learn these techniques and to troubleshoot analytical problems associated with the methods. The compounds addressed in this guide are listed in Table I, but many additional compounds are also amenable to these semivolatile methods. Table I includes the compounds cited in the US EPA Methods, as well as some other compounds typically analyzed in environmental samples.
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Extraction
The compounds listed in Table I may be difficult to extract because they fall into different chemical classes (i.e., acidic, basic, neutral, halogenated, oxygenated, polar, non-polar, lowboiling, and high-boiling compounds). Therefore, the extraction method will need to solvate a wide variety of compounds. It also must recover the analytes of interest while removing the interfering non-target contaminants. This limits the choices of cleanup options. A number of sample extraction methods can be applied to these compounds, but only the most common will be addressed in this guide.
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Liquid Samples
For liquid samples, either separatory funnel extraction (US EPA Method 3510) or automated liquid-liquid extraction (US EPA Method 3520) may be used. Separatory funnel extraction is faster and less expensive to set up than the other methods, but it requires continuous operator attention. Automated liquid-liquid extractors run unattended, but are more expensive and, if analyte recovery is lower than allowed, re-extraction by separatory funnel may be required. Alternatively, if the sample forms an emulsion to the degree that acceptable solvent recovery is not possible using a separatory funnel, then some samples will require automated liquidliquid extraction. Solid phase extraction (US EPA Method 3535) also is an option for aqueous samples.
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For separatory funnel extraction, measure up to 1L of water into a 2L separatory funnel and adjust the pH to >11 using 10M NaOH; be careful not to add too much base. Then extract the sample by adding 60mL of dichloromethane and shaking for two minutes. It is critical to shake all samples consistently or variations in extraction efficiency will be observed. The best way to ensure consistency is to use a mechanical separatory funnel shaker, as there often is considerable variation with manual extractions. Allow the dichloromethane layer to settle to the bottom of the funnel and then decant that layer into a collection vessel (i.e., a Kurdena Danish [KD] concentrator, or a Turbo vap or Rapid vap container if using automated concentrators). This extraction step is repeated twice more to get quantitative recovery of all analytes. Collect all three extractions into the same collection vessel and label as base/neutral. Then adjust the water sample to a pH of slightly less than 2 using sulfuric acid (1:1, v/v). Avoid over-acidification because it can result in an acidic extract. Repeat extraction procedure on the water sample as described above, collecting extracts in a separate collection vessel and labeling it as acid fraction. It is critical to remove water from the dichloromethane before you concentrate the extract to final volume. Dichloromethane can hold approximately 11mL of water per liter of dichloromethane. If this water remains in the extract, it will partition out when the volume is reduced. This will result in the dichloromethane boiling off first, leaving water in the collection vessel, and the formation of a two-layer extract. The analyte recoveries will be lower than desired, and the presence of water will interfere with the GC analysis.
Table I. Semivolatile organic compounds listed in US EPA Methods 8270, 525, and 625.
Peak Number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 Compound 2-fluorophenol phenol-d6 phenol bis(2-chloroethyl) ether 2-chlorophenol-d4 2-chlorophenol 1,3-dichlorobenzene 1,4-dichlorobenzene-d4 (ISTD) 1,4-dichlorobenzene benzyl alcohol 1,2-dichlorobenzene-d4 1,2-dichlorobenzene 2-methylphenol (o-cresol) 2,2'-oxybis-(1-chloropropane) 4-methylphenol (p-cresol) N-nitrosodi-n-propylamine hexachloroethane nitrobenzene-d5 nitrobenzene isophorone 2-nitrophenol 2,4-dimethylphenol bis(2-chloroethoxy)methane benzoic acid 2,4-dichlorophenol 1,2,4-trichlorobenzene naphthalene-d8 (ISTD) naphthalene 4-chloroaniline hexachlorobutadiene 4-chloro-3-methylphenol 2-methylnaphthalene hexachlorocyclopentadiene 2,4,6-trichlorophenol 2,4,5-trichlorophenol 2-fluorobiphenyl 2-chloronaphthalene 2-nitroaniline dimethyl phthalate 2,6-dinitrotoluene acenaphthylene 3-nitroaniline acenaphthene-d10 (ISTD) acenaphthene 2,4-dinitrophenol 4-nitrophenol dibenzofuran 2,4-dinitrotoluene diethyl phthalate Peak Number 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 Compound fluorene 4-chlorophenyl phenyl ether 4-nitroaniline 4,6-dinitro-2-methylphenol N-nitrosodiphenylamine 2,4,6-tribromophenol 4-bromophenyl phenyl ether -HCH hexachlorobenzene -HCH pentachlorophenol -HCH (Lindane) phenanthrene-d10 (ISTD) phenanthrene anthracene -HCH carbazole heptachlor di-n-butyl phthalate aldrin heptachlor epoxide fluoranthene endosulfan I pyrene 4,4'-DDE p-terphenyl-d14 dieldrin endrin endosulfan II 4,4'-DDD endrin aldehyde butyl benzyl phthalate 4,4'-DDT endosulfan sulfate endrin ketone methoxychlor 3,3'-dichlorobenzidine benzo(a)anthracene chrysene-d12 (ISTD) chrysene bis(2-ethylhexyl)phthalate di-n-octyl phthalate benzo(b)fluoranthene benzo(k)fluoranthene benzo(a)pyrene perylene-d12 (ISTD) ideno(1,2,3-cd)pyrene dibenz(a,h)anthracene benzo(g,h,i)perylene
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How to Bake Sodium Sulfate
To bake the sodium sulfate, spread it into a glass pie plate no more than 1" thick and place into a muffle furnace at 400C for a minimum of two hours. After this time, the sodium sulfate should be placed into a glass container while still hot and sealed with a PTFE -lined cap to prevent the material from readsorbing contaminants from the atmosphere.
The optimum way to remove the water is to decant the dichloromethane through granular sodium sulfate, which is held in a funnel with a high-quality grade filter paper (e.g., Whatman 541). Approximately 30g of sodium sulfate are sufficient for most samples. This step must not be skipped. Methods may call for powdered sodium sulfate, but some analytes can be adsorbed onto the smaller particles so it is recommended that only 10-60 mesh or similar granular sodium sulfate be used. Also, it is important that this material be contaminant-free, so it should be purchased as American Chemical Society (ACS) pesticide residuegrade in glass containers or baked in a muffle furnace if purchased in bulk packages where exposure to plastic is an issue (see Restek Tip). If a muffle furnace is not available, the sodium sulfate can be washed or extracted with dichloromethane prior to use; however this technique uses large amounts of solvent.
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Automated liquid-liquid extraction can run unattended once the samples are ready and the solvent is added. This extraction is performed at a single pH. Generally, you will need to adjust the sample pH to 2, but some methods call for adjusting the pH to 4. In any event, it is critical to not let the pH go below 2 when using a liquid-liquid extractor. If this happens, an acidic extract will form and may cause damage to the GC column. Acidic extracts also will cause low recoveries for the late-eluting internal standards, possibly due to isotope exchange (e.g., perylene-d12). Automated liquid-liquid extractors are available in two versionsconventional and accelerated. The conventional types use 1L of sample and extract using 100 to 500mL of dichloromethane. These extraction vessels typically are operated for 16 to 24 hours in order to achieve complete extraction. The accelerated extractor uses a hydrophobic membrane to separate the aqueous from the organic phases, and the extraction time can be reduced by 25 to 30% compared to the conventional extractor. However, the membranes are expensive, so it is important to analyze the cost versus the number of samples extracted to determine if there is a cost benefit to using this accelerated technique. Finally, solid phase extraction (SPE) also may be used to extract semivolatile organic compounds from aqueous samples. When using SPE, it is extremely important to follow the manufacturers recommendations for product use. There are several manufacturers of C18 cartridges and disks, which are the typical media for these compounds. The specific steps to extract these compounds will vary somewhat depending on the manufacturer. One of the biggest problems with SPE is plugging of the disk or tube with suspended solids, so this method only works reliably for drinking water samples. If contamination levels are low and the samples are free of solids, SPE provides very fast extraction times and low solvent usage. It is used easily for field extractions. And, generally, the disks are preferred for the extraction of 1L sample volumes, but recoveries are not uniform for all of the compounds in Table I. The compounds listed in US EPA Method 525.2 exhibit good extraction recoveries using this technique. For detailed information on this extraction, request the Applications Note SPE Extraction for US EPA Method 525.1 (lit. cat.# 59557).
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Clean Glassware
It is important to properly clean glassware used during sample extraction. Contaminated glass surfaces can react with samples and cause breakdown or adsorption of active compounds. Verify cleanliness by running blanks through all glassware.
Soil Samples
Soxhlet and ultrasonic extraction are the most common extraction techniques for solid samples; although pressurized fluid, microwave, and supercritical fluid extraction (SFE) also can be used. Because the soil and biota samples essentially are wet particles, acetone and dichloromethane (1:1) usually are used as the extraction solvents. Acetone is needed to adequately penetrate the soil particle so that compounds in the particle can be extracted. Several other solvent systems are used for more specialized extractions, but for most applications this combination works well. All solvents used for extractions must be ACS pesticide-residue grade, and a solvent assay should be performed to verify purity prior to use. To perform a solvent assay, evaporate 300 to 400mL of solvent to a final volume of 1mL and analyze by GC/mass spectrometry (MS). The resulting chromatogram should have no compounds quantitated above 1/2 the detection limit for any target compound. Soxhlet and ultrasonic extraction work well for the semivolatile compounds listed in Table I. Sonication is a faster technique but requires constant operator attention. In both techniques, problems usually are caused by contaminated reagents (especially sodium sulfate) or by inconsistent handling from sample to sample. Sodium sulfate must be treated to remove water as described in the Restek Tip on page 3, and the sample must be mixed with the sodium sulfate to achieve a sandy consistency. Pressurized fluid extraction (US EPA Method 3545A) can be run in an unattended fashion with multiple samples across a wide sample size range. Extraction vessels with volumes of 1 to 100 mL are available. Instruments like the Dionex ASE 200 accommodate wet samples from 1 to 15 grams, and the Dionex ASE 300 will accommodate wet samples from 15 to 50 grams. The volume of the cell needed for wet samples is generally twice the gram weight of the sample being used. For example, if 30-g wet samples are needed, the 66-mL and 100-mL vessels will be adequate for these extractions. This is necessary because a drying agent such
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as diatomaceous earth is added to the sample prior to being loaded into the extraction vessels. The type of samples being extracted as well as the required method detection limits should be considered as part of the evaluation of pressurized fluid extraction. Microwave extraction (US EPA Method 3546) can be useful for automated extraction as well. This method typically performs the extraction of 12 samples simultaneously, but requires slightly more operator handling than the pressurized fluid extraction instruments. Microwave extraction instrumentation is less expensive, but can suffer from the same sample size limitations. Supercritical fluid extraction (SFE) has been promoted for a number of years as a means of solventless extraction for environmental samples. SFE has been added to SW-846 as Methods 3560, 3561, and 3562 but its application is limited. SFE suffers from severe matrixrelated variation, requiring modification of its conditions depending on soil type, water content, sample size, and type of analytes. Doing so ultimately requires additional sample preparation prior to the actual extraction. These requirements, added to the high cost of the instrument, have virtually precluded the use of SFE for environmental sample preparation.
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Stabilizing Dichloromethane
Dichloromethane requires a stabilizer to prevent the formation of hydrochloric acid (HCl). Without a stabilizer, HCl will form and injection of acidic dichloromethane will cause inlet liners and columns to become reactive. There are two types of stabilizers: stabilizers that keep HCl from forming, and stabilizers that eliminate HCl upon formation. Methanol is a stabilizer that prevents HCl from forming; whereas cyclohehane, cyclohexene, 2methylbutene, and amylene scavenge the HCl after its formation. Dichloromethane used in liquid extractors should contain both types of stabilizers. Methanol is a better stabilizer, acting as a free radical inhibitor, but methanol partitions into the the water phase. This could leave an unstabilized extract unless a scavenger stabilizer also is used.
Cleanup
Sample extract cleanup may be the most important step in maintaining long-term instrument performance. Many times, when instrument problems arise, they are caused by exposure of the injection port and the column to material in the sample extracts other than the target compounds. While all contaminants cannot be eliminated, reducing them will minimize injection port and column maintenance. Most semivolatile extracts, especially those extracts from soil and biota samples, contain high-boiling hydrocarbons and lipids. The difficulty in attempting to remove these compounds using one of the common solid-liquid cleanup techniques (e.g., Florisil and silica gel) is that the cleanup technique also removes some of the target compounds. In addition, because the analytical method usually calls for the reporting of several tentatively identified compounds (TICs), it is not desirable to clean the extracts of compounds that would normally elute in the range of the target compounds. For these reasons, gel permeation chromatography (GPC) is the only universal cleanup technique for semivolatile extracts.
Gel Permeation Chromatography

Gel permeation chromatography (GPC) is a preparative scale chromatographic method of separation based on molecular size. Because the target compounds are similar in molecular size, they elute as a band of material and are easily separated from lighter and heavier contaminants. However, GPC systems are expensive and the processing time per sample is between 30 to 70 minutes. For these reasons many laboratories choose not to use GPC. However, it is very efficient for removing sulfur, high molecular weight hydrocarbons, and lipids from semivolatile extracts; and may be prudent for soil and biota samples. Although sulfur can be removed using other techniques such as mercury or activated copper powder, these procedures, especially copper powder, may degrade some of the target compounds and will not remove the high-boiling hydrocarbons or lipids. The lipid content of biota extracts can be significant and may overload most SPE clean-up techniques. If a sample extract with a high lipid content is injected into the GC, the injection port and front of the column will become contaminated quickly. This will result in failure of check standards and the loss of active compounds such as nitroanilines, nitrophenols, carbazole, and pentachlorophenol (PCP). In spite of the added expense and time required for GPC, it is the best alternative for extract cleanup. US EPA Method 3640 details the requirements for GPC cleanup of extracts for semivolatile analysis. One of the important steps of GPC cleanup is to ensure each day that the instrument is within its retention time calibration. Although not required by the method, it is good practice to run a daily calibration check standard before processing the next batch of samples. If a number of samples have been processed that contain large amounts of contamination, the front of the GPC column can become reactive. This typically is observed in the loss of 2,4,6tribromophenol for semivolatile extracts. If the column becomes reactive, injecting blanks may return the system to control and save the time required to change the column.
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Obtaining consistent GPC results begins with the extraction and concentration procedures because slight changes in mobile phase and sample solvent composition can result in some target compounds being uncollected. Because the typical sample solvent for GPC is pure dichloromethane, it is critical that all extracts be reduced to as small a volume as possible before reconstitution in dichloromethane to avoid large amounts of acetone being applied to the column. Soil and biota samples typically are extracted with a solvent mixture of acetone and dichloromethane. It is critical that all extracts be reduced to as small a volume as possible before reconstitution in dichloromethane to avoid large amounts of acetone being applied to the column. Dichloromethane has a lower boiling point than acetone, so it will evaporate first during sample concentration, which will leave nearly 100% acetone in the concentration vessel. If dichloromethane is then added to adjust the extract to volume, there will be significant amounts of acetone introduced to the GPC column. This will lead to solvent shock and the formation of a void will be observed at the front of the column. This, in turn, will affect the retention times of the compounds eluting from the GPC column and ultimately will result in some target compounds being uncollected. Table II lists the common semivolatile compound elution volumes using GPC.
Analysis Calibration Standards

Calibration standards are purchased as mixtures and usually are divided among three to seven separate ampuls due to the cross-reactivity of several compounds. It is important when making the actual working standard that the solution be stored under refrigerated conditions in a Mininert vial (Restek cat.# 21050 and 21051) due to the volatility of some of the compounds. Failure to properly store the calibration standards will result in evaporative loss of the early-eluting compounds and the solvent. This will, in effect, concentrate the late-eluting compounds and cause continuing calibration failure and quantitation errors. Even when stored under the correct conditions, there still will be degradation of some compounds due to crossreactivity. This is observed as a loss of the target compound and commonly occurs with benzidine, 3,3'-dichlorobenzidine, 4-chloroanaline, N-nitrosodiphenylamine, and to a lesser extent with the phenols and other anilines. These standards are stable in the separate ampuls supplied from the manufacturer, but problems arise when all of the compounds are mixed together to make the working calibration standard. Therefore, it is important to monitor the response of the more active compounds and make fresh mixtures when the calibration standards degrade.
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Mixing Calibration Standards
When blending several ampuls to produce a calibration standard, it is important that all the compounds are completely dissolved in the solvent. This is particularly important with some of the high molecular weight polycyclic aromatic hydrocarbons (PAHs) and pesticides that can separate from solution during refrigerated storage. Before opening ampuls containing semivolatile compounds, allow them to warm to room temperature. Some mixtures may require sonication to ensure complete solubility. Follow the manufacturers recommendations for proper handling of the standard mixture. Because some semivolatile compounds are light sensitive, it is recommended that calibration standards be stored in amber vials.
Injection Port Configuration

Several of the compounds listed in Table I are prone to breakdown or adsorption on active surfaces. Typically this will occur in the injection port; therefore, careful attention must be given to the configuration and maintenance of the injection system. On-column injection techniques can eliminate breakdown or adsorption in the injection system and improve chromatographic analysis for drinking water extracts or extracts with little or no non-volatile residues. However, we do not recommend on-column injections for soil and biota extracts or extracts that contain large amounts of non-volatile residue, because the analytical column can be contaminated quickly. The preferred injection technique for analyzing highly contaminated extracts is direct injection, but direct injection can cause solvent peak tailing and result in some of the target compounds eluting close to the solvent peak. To reduce solvent peak tailing, splitless injection is most commonly used for GC/MS analysis of semivolatile compounds. There are some drawbacks to splitless injection including molecular weight discrimination, incomplete sample transfer, and reactivity. These problems can be minimized if the technique is properly optimized. Splitless injection requires an injection system that is equipped with a solenoid valve controlling the flow to a split vent. The solenoid valve is closed during the injection process, so the majority of the vaporized sample moves to the front of
Table II. Mobile phase volumes for elution of semivolatile compounds by GPC.
Compound 2-fluorophenol phenol-d5 phenol bis(2-chloroethyl)ether 2-chlorophenol-d4 2-chlorophenol 1,3-dichlorobenzene 1,4-dichlorobenzene-d4 1,4-dichlorobenzene 1,2,-dichlorobenzene-d4 1,2-dichlorobenzene 2-methylphenol 2,2'-oxybis(1-chloropropane) 4-methylphenol N-nitroso-di-n-propylamine hexachloroethane nitrobenzene-d5 nitrobenzene isophorone 2-nitrophenol 2,4-dimethylphenol bis(2-chloroethoxy)methane 2,4-dichlorophenol 1,2,4-trichlorobenzene naphthalene-d8 naphthalene 4-chloroaniline hexachlorobutadiene 4-chloro-3-methylphenol 2-methylnaphthalene hexachlorocyclopentadiene 2,4,6-trichlorophenol 2,4,5-trichlorophenol 2-flurorbiphenyl 2-chloronaphthalene 2-nitroaniline dimethylphthalate acenaphthylene 2,6-dinitrotoluene Elution Volumes (mL) Start 201 201 209 201 209 209 225 225 225 225 225 201 201 201 186 233 209 209 193 217 201 193 201 225 225 225 217 225 201 225 225 201 201 217 233 209 193 225 193 End 241 249 225 225 249 241 257 257 257 257 257 241 225 241 217 257 233 233 217 233 225 225 241 257 249 249 241 249 225 249 241 249 249 241 249 233 217 257 225 Compound acenaphthene-d10 3-nitroaniline acenaphthene 2,4-dinitrophenol dibenzofuran 4-nitrophenol 2,4-dinitrotoluene diethylphthalate fluorene 4-chlorophenyl-phenylether 4-nitroaniline 4,6-dinitro-2-methylphenol N-nitrosodiphenylamine 2,4,6-tribromophenol 4-bromophenyl-phenylether hexachlorobenzene pentachlorophenol phenanthrene-d10 phenanthrene anthracene carbazole di-n-butylphthalate fluoranthene pyrene terphenyl-d14 butylbenzylphthalate benzo(a)anthracene 3,3'-dichlorobenzidine chrysene-d12 chrysene bis(2-ethylhexyl)phthalate di-n-octylphthalate benzo(b)fluoranthene benzo(k)fluoranthene benzo(a)pyrene perylene-d12 indeno(1,2,3-cd)pyrene dibenz(a,h)anthracene benzo(g,h,i)perylene Elution Volumes (mL) Start End 225 209 225 201 225 201 201 186 225 217 201 201 201 217 217 233 209 225 225 225 225 178 225 225 217 178 225 209 225 225 162 162 225 225 225 249 241 225 233 249 225 249 225 249 217 225 209 241 241 225 225 233 249 241 257 249 257 257 257 257 201 257 257 233 201 257 241 257 257 186 186 265 265 265 273 273 257 273
Standard prepared and loaded as 1/4 acetone, dichloromethane; 5mL sample loop; Column: 70g SX-3 silica size exclusion packing; Guard column: 5g same packing; Flow rate: dichloromethane at 5.3mL/min. at 13 psi; Samples analyzed by GC/MS. (US EPA 8270 )
the column. After a short time the solenoid valve is opened to allow excess solvent vapor to exit the split vent. The process of transferring the sample onto the column is relatively slow during splitless injection, so the sample must recondense at the front of the column through solvent or analyte focusing. This is accomplished by having the starting oven temperature 20C lower than the boiling point of the solvent or the first eluting compound.
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The time period that the solenoid valve is closed is referred to as the splitless hold-time. The hold-time must be optimized to obtain the best performance from the analytical system. If the solenoid valve is opened too quickly, some of the sample will be lost causing reduced response. If the solenoid valve is open too long, the solvent peak will tail. The splitless holdtime will vary depending on column flow rate, injection port geometry, injection port temperature, and volatility of the analytes. It is impossible to predict the optimum splitless hold-time without performing some experimentation under the exact conditions of your analysis.
Figure 1. Optimizing splitless hold time.
component area (thousands)
20 16 12 8 4 0 0 15 30
early-eluting compounds
late-eluting compounds
45 60 75 hold time (sec.)
90
105
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To optimize the splitless hold time for a particular instrument, prepare a standard that contains both an early- and a late-eluting compound (e.g., fluorophenol and benzo(g,h,i)perylene). Inject this standard over a range of splitless hold times from 0.1 to 2.0 minutes and plot the data. An example of this optimization is shown in Figure 1. In this example the optimum splitless hold time is 60 seconds. This is the point on the graph where the response of the late-eluting compound levels off. Holding the solenoid valve closed longer will not appreciably increase the response of this compound, but will greatly increase the size of the solvent peak. Because the lower boiling compound will transfer onto the column faster, its response will level off sooner (in this example ~45 seconds). Once this data has been plotted, it is possible to observe the correct splitless hold-time (once again, the point at which the response of the late-eluting compounds levels off). The net effect of this optimization is to maximize response of late-eluting compounds while minimizing solvent tailing. In addition to optimizing the splitless hold-time, fused-silica wool should be used in the injection port liner to improve vaporization of higher molecular weight compounds. While there are different theories regarding the placement of fused-silica wool, consistency in the amount of packing and location of the packing is most important. Restek recommends placing the plug of wool below the point that the syringe needle reaches, but above the inlet of the column. We also recommend using a gooseneck liner to minimize contact between the injected sample and the bottom of the injection port. This will help improve the response of the more reactive compounds such as 2,4-dinitrophenol, PCP, and the nitroanalines. The gooseneck liner also makes the greatest improvement in response and minimization of endrin breakdown for US EPA Method 525. Another technique to minimize molecular weight discrimination is to perform the splitless injection under a higher column head pressure. A high inlet pressure is advantageous during injection to control the rapidly expanding vapor cloud in the inlet. By using a momentary pressure pulse for the time that the split vent line is closed, the sample vapor cloud is controlled and sample backflash into the gas lines entering and exiting the injection port is minimized. The effect of the pressure pulse is to increase the amount of analyte transferred to the column, especially the late-eluting components. This can lead to stationary phase overload, however, so it may be necessary to increase the capacity of the column when using this technique (see the Column Selection section for more information).
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Any injection technique can suffer from reactivity (i.e., breakdown) and splitless injection is no exception. The splitless technique has two primary mechanisms for compound reactivity: sample backflash into the gas lines that enter and exit from the injector; and exposure of the sample extract to active sites on the wool, liner, and tip of the column. In general, the same set of compounds break down regardless of which mechanism is occurring: 2,4-dinitrophenol, PCP, 4-nitrophenol, carbazole, and 3-nitroaniline. Daily maintenance of the injection port will help decrease this problem. Replace the inlet liner and fused silica wool plug, and the septum every day. Weekly, or more often depending on the extract contamination level, replace the inlet seal and remove a short section from the front of the column. The length of column removed will vary depending on the level of contamination in the extracts, generally 6 to 12 inches is adequate. When cutting the column and re-installing it into the injection port, be sure to make a square cut and be consistent with the installation distance. The installation distance varies by manufacturer. Refer to Table III for a list of recommended insertion distances.
Table III. Recommended installation distances. Agilent (HP): Varian 1075/1077: PerkinElmer Autosystem: Shimadzu 14A: Shimadzu 17A: split: splitless: 5-7mm from tip of ferrule 5.7cm from back of nut 4.5 - 5.0cm from back of nut 4.0cm from back of nut 35mm from tip of ferrule 40mm from back of nut 64mm from back of nut
Column Selection
Due to the wide variation in functionality, volatility, and polarity of semivolatile compounds, it is not possible to select a column that is highly selective for all of them. As a result, this analysis is performed on a general-purpose stationary phase. The Rtx-5Sil MS column has the best combination of low bleed, high inertness, and efficiency for semivolatile applications. (The Rtx-5MS column also has been successfully used for analysis of semivolatile compounds.) The Rtx-5Sil MS column features a silarylene phenyl/methyl phase that was developed to provide lower bleed and greater efficiency than other 5-type phases for improved separation of the PAHs (Figure 2). Low-bleed columns are necessary for the more sensitive instruments. For laboratories using the Agilent 5973 GC/MS or ion trap MS, column bleed can be a very important issue. As these instruments have become more sensitive, the higher-bleed columns produce a larger signal on the detector and can cause electron multiplier saturaFigure 2. The Rtx-5Sil MS column structure. tion. If this occurs, calibration curves may show non-linearity at higher concentrations. This is sometimes referred to as high-end roll-off, when the signal for a given concentration is lower than expected due to detector saturation. (See Quantitation section for more information on high-end roll-off.) To diagnose column bleed problems, make an injection that allows the bleed to be measured relative to the concentration of the analyte in the method. Many data systems will normalize the display to the largest peak in the analysis. If no compounds are injected, the display will falsely indicate a high background. The Rtx-5Sil MS column shows a minimal bleed level for a 20ng per component standard (Figure 3).
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Figure 3. The Rtx-5Sil MS column exhibits low bleed at 20ng concentration level.
4 1. 2. 3. 4. 5. 6. 7. benzo(b)fluoranthene benzo(k)fluoranthene benzo(a)pyrene perylene-d12 indeno(1,2,3-cd)pyrene dibenz(a,h)anthracene benzo(g,h,i)perylene 5 6 7
12 3
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min.
30m, 0.25mm ID, 0.5m Rtx-5Sil MS (cat# 12738) 20ng splitless injection of CLP standard; GC: HP/Agilent 6890 w/ 5973 mass selective detector, scan range 35-550 AMU; Oven program: 40C (hold 2 min.) to 290C @ 20C/min. (hold 0 min.) to 303C @ 2C/min. (hold 0 min.) to 330C @ 6C/min. (hold 1 min.); Carrier gas: He @ 1.0mL/min. constant flow; Inj. temp.: 300C; Det. temp.: 280C
Detector saturation also can be caused by the concentration of the analytes. It was common practice on older, less sensitive GC/MS systems to increase the multiplier voltage above the tune value to improve sensitivity of low-concentration standards. This technique can lead to problems with the newer, more sensitive instruments. It is much more likely the higher concentration calibration standards will saturate the new GC/MS systems. It may be necessary to reduce the multiplier voltage below the tune value if high-end roll-off is observed. High-end roll-off also may be observed when using pressure-pulsing injection techniques to minimize high molecular weight discrimination. If this is observed, you may either increase the stationary phase film thickness, or increase the column diameter. Alternatively, you may modify the injection conditions to eliminate the source of the overload. Column capacity also must be addressed when optimizing the analysis. The typical calibration range for many of these methods is 20 to 160ng per compound. This requires a column stationary phase and diameter that will not overload with a 160ng or larger injection. Because there is a loss of analyte in any splitless injection, calculation of the necessary column capacity is not simple. If the injection has been optimized for splitless hold-time and fused silica wool is being used in the liner to minimize high molecular weight discrimination, then it is easier to overload the analytical column. Possibly the biggest cause of overload is from pressure-pulsing the injection port, as this improves the transfer of all compounds to the column. The required capacity for your system will be a function of the specific calibration standards and, more importantly, the injection port. From a capacity consideration, a 0.25mm ID column with 0.25m film thickness does not have sufficient capacity for a 160ng per component standard. Figure 4a shows the poor peak shape observed when a column is overloaded. Increased capacity can be achieved by increasing column diameter or film thickness. When increasing column diameter, the flow rate of the column can be a concern with bench-top GC/MS systems. Many bench-top GC/MS systems do not have the pumping capacity for the carrier gas flow that is needed with a 0.32mm ID column. A 0.28mm ID column can increase sample capacity without exceeding the pumping capacity of most bench-top GC/MS systems, making it ideal for calibrating semivolatile compounds from 20 to 160ng without overload. Alternatively, a 0.25mm ID column with a 0.5m film thickness also has sufficient capacity to handle a calibration from 20 to 160ng without exhibiting overload. Figure 4b shows excellent peak shape for a 160ng-per-component standard on a 30m, 0.25mm ID, 0.5m Rtx-5Sil MS column. The total analysis time should be as short as possible without sacrificing separation or resolution between compounds with similar mass spectra. Pay particular attention to the separation between benzo-b- and benzo-k-fluoranthrenethey tend to be the most difficult-
11
Figure 4a & 4b. Avoid overload by selecting a column with the proper capacity.
1 2 4 5 6,7 8 3
Peak List for Fig. 4a & 4b 1. di-n-octyl phthalate 2. benzo(b)fluoranthene 3. benzo(k)fluoranthene 4. benzo(a)pyrene 5. perylene-d12 6. indeno(1,2,3-cd)pyrene 7. dibenz(a,h)anthracene 8. benzo(ghi)perylene Conditions for Fig. 4a 30m, 0.25mm ID, 0.5m Rtx-5Sil MS (cat.# 12738) 160ng splitless injection of CLP standard; GC: HP/Agilent 6890 w/ 5973 mass selective detector, scan range 35550 AMU; Oven program: 40C(hold 2 min.) to 290C @ 20C/min. (hold 0 min.) to 303C @ 2C/min. (hold 0 min.) to 330C @ 6C/min. (hold 1 min.); Carrier gas: He @ 1.0 mL/min. constant flow; Inj. temp.: 300C; Det. temp.: 280C Conditions for Fig. 4b 30m, 0.25mm ID, 0.25m Rtx-5Sil MS (cat.# 12723) unknown concentration (>160ng) splitless injection of CLP standard; GC: HP/Agilent 6890 w/ 5973 mass selective detector, scan range 35-550 AMU; Oven program: 40C (hold 2 min.) to 245C @ 25C/min. (hold 0 min.) to 330C @ 6C/min. (hold 5 min.); Carrier gas: He @ 1.0 mL/min. constant flow; Inj. temp.: 300C; Det. temp.: 280C
4a
Poor peak shape for a 0.25mm ID, 0.25m Rtx-5Sil MS column
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Excellent peak shape for a 0.25mm ID, 0.5m Rtx-5Sil MS column
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to-separate analytes, sharing common mass spectra and quantitation ions. Figure 5 shows a 80ng per component injection of the compounds listed in Table I with an analysis time under 30 minutes. The expanded sections of the chromatogram show the excellent resolution that can be achieved with the Rtx-5Sil MS column. In the past, the GC/MS systems used for semivolatile analysis did not have the sensitivity for split injections, so laboratories were limited to splitless injection. Newer systems such as the Agilent 5973 and ion trap GC/MS have greatly improved sensitivity, which allow the use of split injection and still meet the detection limits required by most semivolatile methods. Figure 6 shows the 20ng per component standard injected in split mode using a 20:1 split ratio on a 30m, 0.25mm ID, 0.25m Rtx-5Sil MS column. The low bleed exhibited by this column is critical when working with these more sensitive GC/MS systems. A benefit of split injection is narrower peak widths for improved separations between closely eluting compounds. Also, split injections usually result in less reactive compound breakdown because the residence time in the injection port is much shorter than in splitless injection. If the sensitivity of an instrument allows for split injection, then column capacity is not nearly the issue it is for splitless injection. Figure 7 shows a 160ng-per-component standard injected under the same conditions as shown in Figure 6. A column with a thinner film can be used because the concentration reaching the column is reduced by 20-fold. The analytical system using split injection will be able to handle higher concentrations of contaminants and possibly stay calibrated longer, but there will be a sacrifice in method detection limits (MDLs). Therefore, it is important to ensure that the MDLs specified in a particular method still can be met if split injection is used.
12
Figure 5. A 30m, 0.25mm ID, 0.5m Rtx-5Sil MS column offers excellent resolution of 106 compounds listed in less than 25 minutes.
47 30m, 0.25mm ID, 0.5m Rtx-5Sil MS (cat# 12738) 10 4 6,7 34 58 89 67 81 82 84 90 91 1,2 5 3 83 86 92 102 103 94 98 100 99 101 104,105 106 87,88 85 93 95,96 97 80ng splitless injection of CLP standard; GC: HP/Agilent 6890 w/ 5973 mass selective detector; Oven program: 40C (hold 2 min) to 290C @ 20C/min. (hold 0 min.) to 303C @ 2C/min. (hold 0 min.) to 330C @ 6C/min. (hold 1 min.); Carrier gas: He @ 1.0 mL/min. constant flow; Inj. temp.: 300C; Det. temp.: 280C, scan range 35-550 AMU 19.0 19.5
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10,11 16,17 34 6,7 20 21,22 13,14 12 29,30 26 31 33 19 37 43 50 8 54 53 59 60 32 18 9 15 23 24 25 38 40 35,36 46 39 45 48 5152 57 64 73 77 76 79 78 61 49 44 27,28 41 42 55 58 62,63 67 68,69 72 66 71 70 65 74 80 81
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N-nitrosodimethylamine pyridine methyl methanesulfonate 2-fluorophenol ethyl methanesulfonate phenol-d6 phenol aniline bis(2-chloroethyl)ether 2-chlorophenol 2-chlorophenol 1,3-dichlorobenzene 1,4-dichlorobenzene-d4 1,4-dichlorobenzene benzyl alcohol 1,2-dichlorobenzene-d4 1,2-dichlorobenzene 2-methylphenol bis(2-chloroisopropyl)ether 4-methylphenol/3-methylphenol N-nitroso-di-n-propylamine
acetophenone hexachloroethane nitrobenzene-d5 nitrobenzene isophorone 2,4-dimethylphenol 2-nitrophenol benzoic acid bis(2-chloroethoxy)methane 2,4-dichlorophenol 1,2,4-trichlorobenzene naphthalene-d8 naphthalene 2,6-dichlorophenol 4-chloroaniline hexachloropropene hexachlorobutadiene 4-chloro-3-methylphenol isosafrole 2-methylnaphthalene 1-methylnaphthalene
hexachlorocyclopentadiene 1,2,4,5-tetrachlorobenzene 2,4,6-trichlorophenol 2,4,5-trichlorophenol 2-fluorobiphenyl safrole 2-chloronaphthalene 2-nitroaniline 1,4-naphthoquinone dimethylphthalate 1,3-dinitrobenzene 2,6-dinitrotoluene acenaphthylene 3-nitroaniline acenaphthene-d10 acenaphthene 2,4-dinitrophenol 4-nitrophenol pentachlorobenzene 2,4-dinitrotoluene dibenzofuran
2,3,4,6-tetrachlorophenol diethyl phthalate 4-chlorophenyl phenyl ether fluorene 4-nitroaniline 4,6-dinitro-2-methylphenol diphenylamine azobenzene 2,4,6-tribromophenol phenacetin 4-bromophenyl-phenyl ether hexachlorobenzene pentachlorophenol pentachloronitrobenzene dinoseb phenanthrene-d10 phenanthrene anthracene di-n-butylphthalate 4-nitroquinoline-1-oxide isodrin
fluoranthene benzidine pyrene aromite p-terphenyl-d14 chlorbenzilate butyl benzyl phthalate kepone bis(2-ethylhexyl)phthalate 3,3'-dichlorobenzidine benzo(a)anthracene chrysene-d12 chrysene di-n-octyl phthalate benzo(b)fluoranthene benzo(k)fluoranthene benzo(a)pyrene perylene-d12 3-methylcholanthrene indeno(1,2,3-cd)pyrene dibenz(a,h)anthracene benzo(g,h,i)perylene
13
Figure 6. A 20ng split injection shows the extremely low bleed of the Rtx-5Sil MS column.
27,28
42,43
59,60 8,9 50,51
30m, 0.25 mm ID, 0.25m Rtx-5Sil MS (cat.# 12723) 20ng split injection of CLP standard; GC: HP/Agilent 6890 w/ 5973 mass selective detector scan range 35-550 AMU; Oven program: 40C (hold 2 min.) to 245C @ 25C/min. (hold 0 min.) to 330C @ 6C/min. (hold 5 min.); Carrier gas: He @ 1.0 mL/min. constant flow; Inj. temp.: 300C; Det. temp.: 280C
10,11,12 32 4,5,6 2,3 1 62 63 65 64 66 70 67 71 72 73 74 75 77 78 68,69
76 79
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Peak List for Figures 6 & 7

1. 2-fluorophenol 2. phenol-d6 3. phenol 4. bis(2-chloroethyl)ether 5. 2-chlorophenol 6. 2-chlorophenol 7. 1,3-dichlorobenzene 8. 1,4-dichlorobenzene-d4 9. 1,4-dichlorobenzene 10. benzyl alcohol 11. 1,2-dichlorobenzene-d4 12. 1,2-dichlorobenzene 13. 2-methylphenol 14. bis(2-chloroisopropyl)ether 15. 4-methylphenol/3-methylphenol 16. N-nitroso-di-n-propylamine 17. hexachloroethane 18. nitrobenzene-d5 19. nitrobenzene 20. isophorone 21. 2-nitrophenol 22. 2,4-dimethylphenol 23. benzoic acid 24. bis(2-chloroethoxy)methane 25. 2,4-dichlorophenol 26. 1,2,4-trichlorobenzene 27. naphthalene-d8 28. naphthalene 29. 4-chloroaniline 30. hexachlorobutadiene 31. 4-chloro-3-methylphenol 32. 2-methylnaphthalene 33. hexachlorocyclopentadiene 34. 2,4,6-trichlorophenol 35. 2,4,5-trichlorophenol 36. 2-fluorobiphenyl 37. 2-chloronaphthalene 38. 2-nitroaniline 39. dimethylphthalate 40. 2,6-dinitrotoluene 41. acenaphthylene 42. acenaphthene-d10 43. 3-nitroaniline 44. acenaphthene 45. 2,4-dinitrophenol 46. 4-nitrophenol 47. dibenzofuran 48. 2,4-dinitrotoluene 49. diethyl phthalate 50. 4-chlorophenyl phenyl ether 51. fluorene 52. 4-nitroaniline 53. 4,6-dinitro-2-methylphenol 54. diphenylamine 55. 2,4,6-tribromophenol 56. 4-bromophenyl-phenyl ether 57. hexachlorobenzene 58. pentachlorophenol 59. phenanthrene-d10 60. phenanthrene 61. anthracene 62. carbazole 63. di-n-butylphthalate 64. fluoranthene 65. pyrene 66. p-terphenyl-d14 67. butyl benzyl phthalate 68. benzo(a)anthracene 69. chrysene-d12 70. chrysene 71. bis(2-ethylhexyl)phthalate 72. di-n-octyl phthalate 73. benzo(b)fluoranthene 74. benzo(k)fluoranthene 75. benzo(a)pyrene 76. perylene-d12 77. indeno(1,2,3-cd)pyrene 78. dibenz(a,h)anthracene 79. benzo(ghi)perylene
59 8,9 50,51
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Figure 7. Analyzing semivolatile compounds in the split injection mode can improve peak shape and eliminate column overload.
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30m, 0.25mm ID, 0.25m Rtx-5Sil MS (cat.# 12723) Sample: 160ng split injection of CLP standard; GC: HP/Agilent 6890 w/ 5973 mass selective detector, scan range 35-550 AMU; Oven program: 40C(hold 2 min.) to 245C @ 25C/min. (hold 0 min.) to 330C @ 6C/min. (hold 5 min.); Carrier gas: He @ 1.0mL/min. constant flow; Inj. temp.: 300C; Det. temp.: 280C
19 20
21
38 58 46 45 59
Resteks Technical Service Team is always here to help. Call us at 800-356-1688 or 814-353-1300, ext. 4, or email us at support@restek.com (U.S.) or intltechsupp@restek.com (outside the U.S.)
10.5 min.
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?
Questions?
Peak list on page 13
15
Reducing Discrimination
Reduced response of the higher molecular weight semivolatile compounds can be caused by discrimination in the injection port. In extreme cases response for the last three PAH compounds may be lost completely at lower calibration levels. To reduce the effects of discrimination in the injection port, we recommend using a drilled Uniliner inlet liner. Because the column seals into the taper at the bottom of the liner, there is reduced loss of high molecular weight compounds and improved response. The drilled Uniliner inlet liner has a small hole drilled at the entrance that allows it to work with small diameter columns and Electronic Pressure Control (EPC) injection systems. When using the drilled Uniliner liner (Figure 8), the response of the last three PAHs is significantly higher compared to the same analysis done with a normal splitless sleeve (see Figure 5). The drilled Uniliner is available for Agilent 5890 and 6890 GCs (see page 19). Figure 8. The Rtx-5Sil MS combined with the Siltek drilled Uniliner liner exhibits excellent peak shape and response for the semivolatile compounds listed in US EPA Method 8270.
GC_EV00576
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26.
N-nitrosodimethylamine pyridine methyl methanesulfonate 2-fluorophenol ethyl methanesulfonate phenol-d6 phenol aniline bis(2-chloroethyl)ether 2-chlorophenol 1,3-dichlorobenzene 1,4-dichlorobenzene-d4 1,4-dichlorobenzene 1,2-dichlorobenzene benzyl alcohol 2-methylphenol bis(2-chloroisopropyl)ether acetophenone 4-methylphenol/3-methylphenol N-nitroso-di-n-propylamine hexachloroethane nitrobenzene-d5 nitrobenzene isophorone 2-nitrophenol 2,4-dimethylphenol
27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52.
bis(2-chloroethoxy)methane benzoic acid 2,4-dichlorophenol 1,2,4-trichlorobenzene naphthalene-d8 naphthalene 2,6-dichlorophenol 4-chloroaniline hexachloropropene hexachlorobutadiene 4-chloro-3-methylphenol isosafrole 2-methylnaphthalene 1-methylnaphthalene hexachlorocyclopentadiene 1,2,4,5-tetrachlorobenzene 2,4,6-trichlorophenol 2,4,5-trichlorophenol 2-fluorobiphenyl safrole 2-chloronaphthalene 2-nitroaniline 1,4-naphthoquinone dimethylphthalate 1,3-dinitrobenzene 2,6-dinitrotoluene
53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 64. 65. 66. 67. 68. 69. 70. 71. 72. 73. 74. 75. 76. 77. 78.
acenaphthylene acenaphthene-d10 3-nitroaniline acenaphthene 2,4-dinitrophenol pentachlorobenzene 4-nitrophenol dibenzofuran 2,4-dinitrotoluene 2,3,4,6-tetrachlorophenol diethyl phthalate fluorene 4-chlorophenyl phenyl ether 4-nitroaniline 4,6-dinitro-2-methylphenol diphenylamine azobenzene 2,4,6-tribromophenol phenacetin 4-bromophenyl phenyl ether hexachlorobenzene pentachlorophenol pentachloronitrobenzene phenanthrene-d10 dinoseb phenanthrene
79. 80. 81. 82. 83. 84. 85. 86. 87. 88. 89. 90. 91. 92. 93. 94. 95. 96. 97. 98. 99. 100. 101. 102. 103. 104.
anthracene di-n-butylphthalate 4-nitroquinoline-1-oxide isodrin fluoranthene benzidine pyrene p-terphenyl-d14 aramite chlorbenzilate kepone butyl benzyl phthalate benzo(a)anthracene 3,3'-dichlorobenzidine chrysene-d12 chrysene bis(2-ethylhexyl)phthalate di-n-octyl phthalate benzo(b)fluoranthene benzo(k)fluoranthene benzo(a)pyrene perylene-d12 3-methylcholanthrene indeno(1,2,3-cd)pyrene dibenzo(a,h)anthracene benzo(g,h,i)perylene
30m, 0.25mm ID, 0.25m Rtx-5Sil MS (cat.# 12723) Conc.: 24g/mL in methylene chloride (cat.#s: 31618, 31619, 31620, 31621, 31622, 31206, 31062, 31063) Note: Internal standards at 8 ppm Inj. vol.: Inj type: Hold time: Inlet liner: Inj. temp.: Carrier gas: Linear velocity: Oven temp.: 1L splitless 0.4 min. drilled Uniliner liner, Siltek deactivation (cat# 21054-214.1) 300C helium (1mL/min. constant flow) 34cm/sec. 35C (hold 2 min.) to 260C @ 20C min. (hold 0 min.), to 330 @ 6C/min. (hold 1 min.) MS 280C 35 to 550amu EI full scan
Det. type: Transfer line temp.: Scan range: Ionization: Mode:
16
Quantitation
Because splitless injections suffer from irreproducibility, quantitation for semivolatile compounds is by internal standard, using a single ion for each analyte. Internal standards at known concentrations are used to correct for variances in the amount of material transferred to the column with different injections, and also to track MS sensitivity. All sample analyte concentrations are calculated using response factors obtained from the calibration curve. This method uses single ions (i.e., extracted ions) for each compound so that chromatographic resolution of each compound is not necessary. It is acceptable for compounds to co-elute, as long as they do not have any common ions used for quantitation. Typically, only isomers have similar spectra, so chromatographic resolution is required only for these compounds. Figure 9 shows the possibilities for calibration curves for this analysis. Curve A is the desired result, indicating a proportional response with increasing concentration. This implies that there is no detector saturation or reactivity for this compound. Curve B is indicative of a compound that undergoes a reaction, usually in the injection port or on the head of the column. If a calibration curve like Curve B is observed, injection port or column maintenance is required. Finally, Curve C shows high-end roll-off, indicating saturation. If a calibration Figure 9. Calibration curves showing linear response, adsorption, and high-end roll-off.
200000
responce (area counts)
180000 160000 140000 120000 100000 80000 60000 40000 20000 20 40 90 80 100 120 140
C A
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curve like Curve C is observed, select a column with higher capacity or reduce detector sensitivity by lowering the multiplier voltage.
Summary
Although the analysis of semivolatile organic compounds is one of the more difficult tests performed by environmental laboratories, using Resteks Rtx-5Sil MS or Rtx-5MS columns and following the tips presented in this guide can make it easier to perform. Correct sample preparation, extract cleanup, injection technique, analytical columns, standards, and quantitation can help minimize problems normally associated with semivolatile organic analyses. When problems occur, use the most appropriate troubleshooting and maintenance procedures to quickly optimize your analytical system. When faced with difficulties in your semivolatile analysis, remember that the majority of problems occur in the sample preparation and cleanup step, or in the GC injection port. If you still are having difficulties after reading through this guide, contact Resteks Technical Service Team via email at support@restekcorp.com or via phone at 800-356-1688 or 814-353-1300, ext. 4.
Rtx-5MS and Rtx-5Sil MS Columns

Conventional capillary gas chromatography (GC) columns use liquid stationary phases, many of which are crossbonded to yield a higher working temperature. Even with crossbonding, however, the liquid stationary phase will slowly elute. This elution of the stationary phase, also termed column bleed, is more detectable at higher temperatures and is typically observed as an increasing baseline that follows the oven temperature program. Depending on the method of detection, column bleed may not be an issue for certain separations. If the capillary column is connected to a sensitive detector like a mass spectrometer (MS), then column bleed can cause a number of problemsspecifically misidentification of analytes, loss of sensitivity, and inaccurate quantitation. The level of column bleed will affect the senstivity of any MS, especially ion trap instruments, which use automatic gain control. As the level of column bleed increases, so does the signal from bleed ions in the mass spectra of analytes and unknowns. Also, sensitivity (or detection limit) severely degrades. The contribution of bleed ions to the mass spectra can result in misidentification of compounds, requiring laboratory personnel to subtract these ions before performing library searches. Doing so can add considerable time to their analyses. Finally, if bleed ions contribute to the signal of the quantitation mass, quantitation of analytes and unknowns will be miscalculated. For these reasons, it is critical that analysts choose the lowest-bleed column designed for GC/MS applications. Many manufacturers offer MS phases for applications requiring low bleed. In many cases, these represent nothing more than the reporting of the bleed signal when the column was tested for a single analysis at the manufacturer. Restek has developed true low-bleed MS phases. These columns exhibit a much lower column bleed than was previously available. The Rtx-5MS column is a low-bleed, dimethyl/diphenyl polysiloxane phase. The Rtx-5Sil MS is a low-bleed silarylene methyl/phenyl phase. The combination of Resteks polymer chemistry and rigorous QA testing ensures that each MS column exceeds requirements of the most sensitive mass spectrometers.
ID 0.25mm
0.32mm
0.53mm
df (m) 0.10 0.25 0.50 1.00 0.10 0.25 0.50 1.00 0.50 1.00 1.50
temp. limits -60 to 330/350C -60 to 330/350C -60 to 330/350C -60 to 325/350C -60 to 330/350C -60 to 330/350C -60 to 330/350C -60 to 325/350C -60 to 320/340C -60 to 320/340C -60 to 310/330C
15-Meter 12605 12620 12635 12650 12606 12621 12636 12651 12637 12652 12667
30-Meter 12608 12623 12638 12653 12609 12624 12639 12654 12640 12655 12670
60-Meter 12611 12626 12641 12612 12627 12642
Rtx-5MS
Fused Silica (Crossbond 5% diphenyl - 95% dimethyl polysiloxane) Stable to 360C
ID 0.25mm
0.28mm
0.32mm
0.53mm
df (m) 0.10 0.25 0.50 1.00 0.25 0.50 1.00 0.10 0.25 0.50 1.00 0.50 1.00 1.50
temp. limits -60 to 330/350C -60 to 330/350C -60 to 330/350C -60 to 325/350C -60 to 330/350C -60 to 330/350C -60 to 325/350C -60 to 330/350C -60 to 330/350C -60 to 330/350C -60 to 325/350C -60 to 320/340C -60 to 320/340C -60 to 310/330C
15-Meter 12705 12720 12735 12750 12790 12791 12792 12706 12721 12736 12751 12737 12752 12767
30-Meter 12708 12723 12738 12753 12793 12794 12795 12709 12724 12739 12754 12740 12755 12770
Fused Silica (equivalent selectivity of Crossbond 5% diphenyl/95% dimethyl polysiloxane) Stable to 360C
Rtx-5Sil MS
18
Innovative Integra-Guard Columns

Integra-Guard built-in guard column Some people swear by press-fit connectors, and others swear at them. For many analysts, the art of attaching a guard column to an analytical column is a mystery. Resteks chemists have discovered the solution to this mysterythe easiest, most reliable connection is no connection at all! No guard column system is more permanent than one continuous length of tubing containing both the guard column and the analytical column. Restek offers a wide variety of Integra-Guard capillary columns with a guaranteed leak-free connection! The guard column is tied separately from the analytical column, using hightemperature string. The transition area between the columns is the point at which the guard column ends and the analytical column begins. The entire setup is suspended in our unique crush-free cage, which prevents the column from coming in contact with anything that could damage it. Ordering is simple. Just add the appropriate suffix number and price to the analytical columns catalog number and price. For example, a 30m, 0.25mm ID, 0.25m Rtx-5MS with a 5m Integra-Guard column is cat.# 12623-124.
ID (mm) 0.25 0.28 Length (m) 5 10 5 10 Suffix # -124 -127 -243 -244 ID (mm) 0.32 0.53 Length (m) 5 10 5 10 Suffix # -125 -128 -126 -129
Phases currently available as Integra-Guard columns: Rtx-1 Rtx-1MS Rtx-5 Rtx-5MS Rtx-5Sil MS XTI-5 Rtx-1301 Rtx-624 Rtx-1701 Rtx-Volatiles Rtx-20 Rtx-35 Rtx-35MS Rtx-BAC 1 & 2 Stabilwax
For analysts who prefer to attach a guard column to the analytical column themselves, Restek offers deactivated guard columns and Press-Tight connectors.
formoreinfo
For detailed information on types of guard columns, their uses, and a complete product listing, request Resteks Guard Column Fast Facts flyer (lit. cat.# 59319)
Intermediate-Polarity Deactivated Guard Columns

Nominal ID (mm) 0.15 0.18 0.25 0.28 0.32 0.45 0.53 Nominal OD (mm) 0.363 0.012 0.37 0.04 0.37 0.04 0.37 0.04 0.45 0.04 0.69 0.05 0.69 0.05 1-Meter 10101 10102 5-Meter 10042 10046 10043 10003 10044 10005 10045
Press-Tight Connectors
Seals all common sizes (0.18 to 0.53mm ID, outside diameters from 0.3 to 0.75mm) of fused silica tubing. Connect guard columns to analytical columns, repair broken columns, or connect column outlets to transfer lines. Angled connectors are designed to approximate the curvature of a capillary column and reduce strain on column-end connections. Made from inert fused silica. Universal Angled Press-Tight Connectors: cat.# 20446 (5-pk.); cat.# 20447 (25-pk.); cat.# 20448 (100-pk.) Universal Press-Tight Connectors: cat.# 20400 (5-pk.); cat.# 20401 (25-pk.); cat.# 20402 (100-pk.) Deactivated Universal Press-Tight Connectors: cat.# 20429 (5-pk.); cat.# 20430 (25-pk.); cat.# 20431 (100-pk.) Universal Y Press-Tight Connectors: cat.# 20405 (ea.); cat.# 20406 (3-pk.) Universal Angled Y Press-Tight Connectors: cat.# 20403 (ea.); cat.# 20404 (3-pk.)
19
Inlet Liners
For Agilent/HP & Finnigan GCs
Splitless Liners for Agilent/HP & Finnigan GCs Benefits/Uses:
trace samples >2L 4mm Splitless trace samples >2L 4mm Splitless w/ FS Wool
ID*/OD & Length (mm)

4.0 ID 6.5 OD x 78.5 4.0 ID 6.5 OD x 78.5 4.0 ID 6.5 OD x 78.5 4.0 ID 6.5 OD x 78.5 2.0 ID 6.5 OD x 78.5 4.0 ID 6.5 OD x 78.5 4.0 ID 6.5 OD x 78.5 4.0 ID 6.5 OD x 78.5 2.0 ID 6.5 OD x 78.5 4.0 ID 6.5 OD x 78.5 4.0 ID 6.3 OD x 78.5 4.0 ID 6.3 OD x 78.5
ea.
20772
cat.# 5-pk.
20773
Similar to 25-pk. Agilent part #

20774
E N D
22400
22401
22402
19251-60540
T H I S
trace samples >2L 4mm Splitless (quartz) trace samples >2L 4mm Splitless (quartz) w/ FS Wool trace samples <2L
20912
20913
18740-80220 5181-8818
22403
22404
20795
20796
20797
I N S T A L L S
Gooseneck Splitless (2mm) trace samples >2L Gooseneck Splitless (4mm) trace samples >2L Gooseneck Splitless (4mm) w/ FS Wool trace, active samples >2L Double Gooseneck Splitless (4mm) trace, active, dirty samples <2L trace, active, dirty samples >2L allows direct injection when using EPC-equipped GC allows direct injection when using EPC-equipped GC
20798
20799
20800
5181-3316
22405
22406
22407
5062-3587
20784
20785
20786
5181-3315
20907
20908
Cyclo Double Gooseneck (2mm)
C O L U M N
20895
20896
20997
Cyclo Double Gooseneck (4mm)
21054
21055
Drilled Uniliner (4mm)
21054-214.1 21055-214.5
Siltek Drilled Uniliner (4mm)
For Varian GCs

Splitless Liners for Varian 1075/1077GCs
C O L U M N I N S TA L L S T H I S E N D
Benefits/Uses:
trace samples<2L
ID**/OD & Length (mm)

2.0 ID 6.3 OD x 74 4.0 ID 6.3 OD x 74 4.0 ID 6.3 OD x 74 4.0 ID 6.3 OD x 74
ea.
20721
cat.# 5-pk. 25-pk.

20722 20723
Similar to Varian Part #

01-900109-05
2mm Splitless trace samples>2L 4mm Splitless trace, active samples up to 4L trace, dirty, active samples up to 4L
20904
20905 20906
01-900109-05
20847
20848 20849
Double Gooseneck
20897
20898
Cyclo Double Gooseneck
1078/1079 Liners for Varian GCs

1078/1079 Splitless
Benefits/Uses:
trace samples <2L
ID**/OD & length (mm)

2.0 ID 5.0 OD x 54
ea.
21711
cat.# 5-pk. 25-pk.

21712
Similar to Varian Part #

03-918466-00
*Nominal ID at syringe needle expulsion point.
20
Inlet Liners
For Shimadzu GCs
Splitless Liners for Shimadzu GCs
94mm Splitless with Wool* reduces backflash and catalytic decomposition reduces backflash, also operates in DI mode
Benefits/Uses:
trace samples

3.5 ID 5.0 OD x 94 3.5 ID 5.0 OD x 94 3.5 ID 5.0 OD x 94
ea.
20955
cat.# 5-pk. 25-pk.

20956 20957
Similar to Shimadzu Part #

221-09145
20958
20959 20960
94mm Double Gooseneck
20961
20962 20963
221-41599-00
94mm Single Gooseneck
For PerkinElmer GCs

Splitless Liners for PerkinElmer GCs
COLUMN INSTALLS THIS END
Benefits/Uses:
trace samples

2.0 ID 6.2 OD x 92.1 3.5 ID 6.2 OD x 92.1 3.5 ID 6.2 OD x 92.1 2.0 ID 4.0 OD x 86.2
ea.
20829
cat.# 5-pk. 25-pk.

20830 20831
Similar to PE Part #
N6101372
Auto SYS Splitless w/Wool (2mm ID)* trace, active samples up to 4L trace, dirty, active samples up to 4L most common analyses
20853
20854
Auto SYS Double Gooseneck
20899
20900
Auto SYS Cyclo Double Gooseneck
21717
21718
N612-1004
Auto SYS XL Split/Splitless
For Thermo Orion GCs

Splitless Liners for 5000-6000 Series GCs
END
Benefits/Uses:
trace samples

4.0 ID 5.5 OD x 79.5
ea.
20814
cat.# 5-pk. 25-pk.

20815 20816
Similar to TO Part #
THIS
Splitless (4mm ID)
I N S TA L L S
Splitless Liners for 8000 & TRACE Series GCs

Splitless (3mm ID)
Benefits/Uses:
trace samples

3.0 ID 8.0 OD x 105 5.0 ID 8.0 OD x 105 4.0 ID 8.0 OD x 105
ea.
20942
cat.# 5-pk. 25-pk.

20943 20944
Similar to TO Part #
453 20032
trace samples Splitless (5mm ID) trace, active samples up to 4L
20945
20946 20947
453 20033
COLUMN
20952
20953
Double Gooseneck
O-Rings
Viton
Viton o-rings are universal. One size fits both split (6.3mm ID) and splitless (6.5mm ID) sleeves.
Viton (fluorocarbon) Max. temp. 350C Similar to Agilent Part # 5180-4182 cat.# 20377 Qty. 25-pk.
Graphite
Graphite o-rings have excellent thermal stability and can be used at injection port temperatures up to 450C!
6.35mm ID for split liners 6.5mm ID for splitless liners Similar to Agilent Part # 5180-4168 5180-4173 10-pk. 20296 20298 50-pk. 20297 20299
*Liner is packed with fused silica wool. To order glass wool instead, add the suffix 202 to the liners catalog number.
**Nominal ID at syringe needle expulsion point.
21
Deactivated Fused Silica Wool

Ensure uniform vaporization in split or splitless liners. Prolong column life by trapping septum particles. Recommended for autosamplers with fast injection rates. Inertness tested for endrin breakdown. cat.# 20790, (10 grams)
free
guide
Request the handy, pocket-sized, Inlet Supplies Guide (lit. cat.# 59893A).
Replacement Inlet Seals

Special grade of stainless steel deforms easily, ensuring a completely leak-free seal. Available in stainless steel, gold-plated, and Silcosteel-treated. Cross-Disk ideal for high-flow split applications on EPC-equipped GCs. Shipped with washers.
For Agilent 5890/6890/6850 Split/Splitless Injection Ports

Single-Column Installation, Opening Size 0.8mm ID Stainless Steel Inlet Seal* 21315, 2-pk. 21316, 10-pk.
Cross-Disk for Agilent GCs

Cross-Disk, Opening Size 0.8mm ID Gold-Plated Inlet Seal 20477, 2-pk.
20476, 10-pk.
Silcosteel Inlet Seal 20475, 2-pk. 20474, 10-pk.
Gold-Plated Inlet Seal** 21317, 2-pk. 21318, 10-pk.
Cross-Disk, Opening Size 1.2mm ID Gold-Plated Inlet Seal 21009, 2-pk.
Silcosteel Inlet Seal 21319, 2-pk. 21320, 10-pk.
21010, 10-pk.
Silcosteel Inlet Seal 21011, 2-pk.
*0.8mm ID stainless steel inlet seal is equivalent to Agilent part #18740-20880. **0.8mm ID gold-plated inlet seal is equivalent to Agilent part #18740-20885.
21012, 10-pk.
Similar to Agilent part #5182-9652.
Thermolite Septa
Each batch tested on FIDs, ECDs, & MSDs to ensure lowest bleed. Excellent puncturability. Preconditioned and ready to use. Do not adhere to hot metal surfaces. Usable to 340C inlet temperatures. Packaged in non-contaminating tins.
Septum Diameter 5mm (3/16") 6mm (1/4") 7mm 8mm 9.5mm (3/8") 10mm 11mm (7/16") 11.5mm 12.5mm (1/2") 17mm Shimadzu Plug 25-pk. 20351 20355 20381 20370 20359 20378 20363 22385 20367 20384 20372 50-pk. 20352 20356 20382 20371 20360 20379 20364 22386 20368 20385 20373 100-pk. 20353 20357 20383 20361 20380 20365 22387 20369 20386 20374
Call our literature hotline at 800-356-1688 or 814-353-1300, ext. 5, or your local Restek representative for Resteks 20-page bulletin, A Guide to Minimizing Septa Problems (lit. cat.# 59886).
free
guide
22
EZ-Vent 2000

EZ-Vent 2000 for Agilent GCs
great idea!
Change GC/MS columns in minutes without venting. Silcosteel treated for greater inertness. Deactivated transfer line minimizes bleed into the source. Stainless steel body and high-temperature polyimide ferrules minimize leaks at the problematic transfer line fitting. Less expensive than other no-vent fittings. 100m transfer line throttles vacuum and prevents column pump down. Available for Agilent GCs with 5971/5972 or 5973 MS and Varian 3400, 3600, or 3800 GCs with Saturn 2000 MS. Precision-machined orifice.
EZ-Vent 2000 for Varian GCs
Kits EZ-Vent 2000 for Agilent GCs with 5971/5972 or 5973 MS Includes EZ-Vent 2000, 1/16" SS nut, 0.4mm ID ferrules for connecting capillary column, 0.4mm ID ferrules for connecting transfer line, 100m deactivated transfer line (3 ft.), and EZ-Vent column plug; cat.# 21013, (kit) EZ-Vent 2000 for Varian Saturn 2000 MS systems with 3400, 3600, or 3800 GCs Includes EZ-Vent 2000, 1/16" SS nut, 0.4mm ferrules for connecting capillary column, 0.4mm ID ferrules for connecting transfer line, 100m deactivated transfer line (3 ft.), and EZ-Vent column plug; cat.# 21014, (kit)
EZ-Vent 2000 ferrules
Ferrules
Capillary Ferrules (for 1/16" compression-type fittings)
Ferrule ID (mm)
0.4 0.4 0.5 0.5 0.6 0.8 0.8
Fits Column ID (mm)

0.25 0.25 0.32 0.32 0.28 0.53 0.53
Qty.
50-pk. 10-pk. 10-pk. 50-pk. 10-pk. 10-pk. 50-pk.
Graphite
20227 20200 20201 20228 20202 20224
Vespel/ Graphite
20229 20211 20212 20231 20232 20213 20230
Compact Ferrules for Agilent GCs

Ferrule ID (mm)
0.4 0.4 0.5 0.5 0.8 0.8
Fits Column ID (mm)

0.25 0.25 0.32 0.32 0.53 0.53
Qty.
10-pk. 50-pk. 10-pk. 50-pk. 10-pk. 50-pk.
Graphite
20250 20251 21007 21008 20252 20253
Vespel/ Graphite
20238 20239 20248 20249 20263 20264
Encapsulated Ferrules
Will not deform and stick in fittings. Reusable. For 1/16" compression fittings.
Ferrule ID
0.4mm 0.5mm 0.8mm
Fits column ID
0.25mm 0.32mm 0.53mm
cat.#/10-pk.
21036 21037 21038
23
Direct Replacement Split/Splitless Injection Ports for Agilent GCs

Would you like better performance from your injector? Resteks Silcosteel-coated split/ splitless injector is a direct replacement for Agilent 5890 and 6890/6850 GCs. The injector is manufactured from high-quality stainless steel and meets or exceeds Agilent original equipment specifica tions. Silcosteel passivates the metal surface to ensure an inert pathway for the sample, delivering increased version available performance.
Weldment for Agilent 5890 GCs
For Agilent 5890 GCs

Description Replacement Weldment (Similar to Agilent part# 19251-60575) Replacement Shell Weldment (Similar to Agilent part# 19251-80570) Silcosteel Weldment Silcosteel Shell Weldment
cat.#, (ea.) 20265 20266 20267 20268
Shell weldment for Agilent 5890 GCs
For Agilent 6890/6850 GCs

Description Replacement Weldment for Agilent 6890/6850 GCs with EPC Replacement Weldment for Agilent 6890/6850 GCs with manual flow Replacement Shell Weldment for Agilent 6890/6850 GCs cat.#, (ea.) 22674 20265 22673
Weldment and shell weldment for Agilent 6890/6850 GCs
MSD Conversion FittingImproved

Uses a flat, soft aluminum sealing ring to deform and butt-seal against the MSD interface (see figure below). A standard Vespel ferrule seals the column and 1/16-inch stainless steel nut. Fitting is constructed of nickel-plated brass for longevity and softness. Can use any standard Vespel or Vespel/graphite 1/16-inch ferrule. Includes a 1/16-inch stainless steel nut and two replacement sealing rings. Order ferrules separately. MSD Conversion Fitting: cat.# 21314, (ea.) MSD Conversion Fitting Replacement Ring Seal: cat.# 21313, (2-pk.)
check it out
Original Agilent Design

S O U R C E S O U R C E
Restek MSD Conversion Fitting
butt-seal with ferrule
only column seals at taper
crunch washer forms leak-free sealeasier to remove
shoulder strength increased
ferrule seals against both column and fitting
Agilents MSD interface requires a butt-seal at the base of a Vespel ferrule, which is prone to leakage. Resteks version uses a standard ferrule design that simultaneously seals the fitting and capillary tubing with compressive forces.
MSD Source Nut

The nut bore has been changed from 0.8mm to 1.2mm to permit easy removal of ferrules with a standard tapered-needle file (cat.# 20106). The nuts still match the manufacturers original part specifications and are made of brass to prevent thread-stripping on the transfer line. (Similar to Agilent part #05988-20066.) (Detector) MSD Source Nut: cat.# 20643, (2-pk.)
24
US EPA Methods 8270C & 8270D Analytical Reference Materials
Internal Standard Mixtures
SV Internal Standard Mix
acenaphthene-d10 crysene-d12 1,4-dichlorobenzene-d4 naphthalene-d8 perylene-d12 phenanthrene-d10
Matrix Spiking Mixtures

B/N Matrix Spike Mix
acenaphthene 1,4-dichlorobenzene 2,4-dinitrotoluene N-nitroso-di-n-propylamine pyrene 1,2,4-trichlorobenzene
4,000g/mL each in methylene chloride, 1mL/ampul
US EPA Method 8270D outlines the analysis of semivolatile organic pollutants in solid waste, soil, water, and air matrices, using GC/MS. Update IVA of the third edition of SW-846Test Methods for Evaluating Solid Waste, Physical/Chemical Methodsincludes EPA Method 8270D, in which there were no major revisions from EPA Method 8270C.
w/data pack
Each 31006 31006-500
5-pk. 31006-510 31006-520
10-pk. 31106 w/data pack
Each 31004 31004-500
5-pk. 31004-510 31004-520
10-pk. 31104
w/data pack
Each 31206 31206-500
5-pk. 31206-510 31206-520
Each 31074 31074-500
5-pk. 31074-510 31074-520
10-pk. 31174
Surrogate Mixtures
B/N Surrogate Mix (4/89 SOW)
2-fluorobiphenyl nitrobenzene-d5 p-terphenyl-d14
w/data pack
Each 31084 31084-500
5-pk. 31084-510 31084-520
10-pk. 31184
Method 8270 Calibration Kits

8270 Calibration Kit
31618: 8270 Calibration Mix #1 31619: 8270 Calibration Mix #2 31620: 8270 Calibration Mix #3 31621: 8270 Calibration Mix #4 31622: 8270 Calibration Mix #5 Contains 1mL each of these mixtures.
Acid Matrix Spike Mix

4-chloro-3-methylphenol 2-chlorophenol 4-nitrophenol pentachlorophenol phenol
w/data pack
Each 31024 31024-500
5-pk. 31024-510 31024-520
10-pk. 31124
kit
w/data pack Kit w/Data Pack 31626-500
Each 31062 31062-500
5-pk. 31062-510 31062-520
Each 31014 31014-500
5-pk. 31014-510 31014-520
10-pk. 31114
Kit 31626
w/data pack
Each 31086 31086-500
5-pk. 31086-510 31086-520
Each 31061 31061-500
5-pk. 31061-510 31061-520
10-pk. 31161
8270/Appendix IX Calibration Kit

31618: 8270 Calibration Mix #1 31619: 8270 Calibration Mix #2 31620: 8270 Calibration Mix #3 31621: 8270 Calibration Mix #4 31622: 8270 Calibration Mix #5 31623: 8270 Calibration Mix #6 31625: Appendix IX Mix #1 Contains 1mL each of these mixtures.
Acid Surrogate Mix (4/89 SOW)

2-fluorophenol phenol-d6 2,4,6-tribromophenol
kit
w/data pack Each 5-pk. 31025 31025-510 31025-500 31025-520 10-pk. 31125
Each 31071 31071-500
5-pk. 31071-510 31071-520
10-pk. 31171
w/data pack
Kit 31627
Kit w/Data Pack 31627-500
GC/MS Tuning Mixture

GC/MS Tuning Mixture
benzidine 4,4'-DDT DFTPP pentachlorophenol
Aramite Mix
2,000ppm each in hexane, 1mL/ampul
w/data pack
Each 5-pk. 31063 31063-510 31063-500 31063-520
10-pk. 31163
w/data pack
Each 31624 31624-500
5-pk. 31624-510 31624-520
Each 5-pk. 31087 31087-510 31087-500 31087-520
Each 31615 31615-500
5-pk. 31615-510 31615-520
10-pk. 31715
25
US EPA Methods 8270C & 8270D Analytical Reference Materials
Calibration Check Compound Mixtures
8270 B/N Calibration Check Mix
acenaphthene benzo(a)pyrene 1,4-dichlorobenzene di-n-octyl phthalate diphenylamine fluoranthene hexachlorobutadiene
Calibration Mixtures
8270 Calibration Mix #3
aramite hexachlorobenzene bis (2-chloroethyl) ether hexachlorobutadiene bis (2-chloroethoxy) methane hexachlorocyclopentadiene bis (2-chloroisopropyl) ether hexachloroethane 4-bromophenyl phenyl ether hexachloropropene chlorobenzilate isodrin 2-chloronaphthalene kepone 4-chlorophenyl phenyl ether pentachlorobenzene 1,2-dichlorobenzene pentachloronitrobenzene 1,3-dichlorobenzene 1,2,4,5-tetrachlorobenzene 1,4-dichlorobenzene 1,2,4-trichlorobenzene 1,3-dinitrobenzene 2,000g/mL each in methylene chloride, 1mL/ampul
diallate (cis & trans) dimethoate disulfoton famphur methyl parathion phosphorothioate parathion phorate pronamide thionazine 0,0,0-triethyl
w/data pack
Each 31616 31616-500
5-pk. 31616-510 31616-520
10-pk. 31716
w/data pack
Each 31623 31623-500
5-pk. 31623-510 31623-520
10-pk. 31723
8270 Acid Calibration Check Mix

4-chloro-3-methylphenol 2,4-dichlorophenol 2-nitrophenol pentachlorophenol phenol 2,4,6-trichlorophenol
Organochlorine Pesticide Mix AB #1

aldrin -BHC -chlordane -BHC 4,4'-DDD 4,4'-DDE 4,4'-DDT -BHC dieldrin endosulfan I endosulfan II endosulfan sulfate endrin endrin aldehyde endrin ketone -BHC (lindane) -chlordane heptachlor heptachlor epoxide (B) methoxychlor
w/data pack
Each 31620 31620-500
5-pk. 31620-510 31620-520
10-pk. 31720
w/data pack
Each 31617 31617-500
5-pk. 31617-510 31617-520
10-pk. 31717

acetophenone azobenzene benzyl alcohol bis (2-ethylhexyl) phthalate butyl benzyl phthalate dibenzofuran diethyl phthalate dimethyl phthalate di-n-butyl phthalate di-n-octyl phthalate 2,4-dinitrotoluene 2,6-dinitrotoluene ethyl methanesulfonate isophorone isosafrole (cis & trans) methyl methanesulfonate 1,4-naphthoquinone nitrobenzene 4-nitroquinoline-1-oxide phenacetin safrole
benzoic acid 4-chloro-3-methylphenol 2-chlorophenol 2,4-dichlorophenol 2,6-dichlorophenol 2,4-dimethylphenol 4,6-dinitro-2-methylphenol 2,4-dinitrophenol dinoseb 2-methylphenol 3-methylphenol 4-methylphenol 2-nitrophenol 4-nitrophenol pentachlorophenol phenol 2,3,4,6-tetrachlorophenol 2,4,5-trichlorophenol 2,4,6-trichlorophenol
200g/mL each in hexane/toluene (1:1), 1mL/ampul
w/data pack
Each 5-pk. 32291 32291-510 32291-500 32291-520
10-pk. 32391
Appendix IX Mix #1
5-pk. 31621-510 31621-520 10-pk. 31721
2-acetylaminofluorene 4-aminobiphenyl p-dimethylaminoazobenzene 3,3'-dimethylbenzidine ,,-dimethylphenethylamine (free base) methapyrilene (free base) 1-naphthylamine 2-naphthylamine 5-nitro-o-toluidine N-nitrosodibutylamine N-nitrosodiethylamine N-nitrosomethylethylamine N-nitrosomorpholine N-nitrosopiperidine N-nitrosopyrrolidine 1,4-phenylenediamine 2-picoline o-toluidine
w/data pack
Each 31621 31621-500

acenaphthene acenaphthylene anthracene benzo(a)anthracene benzo(a)pyrene benzo(b)fluoranthene benzo(ghi)perylene benzo(k)fluoranthene chrysene dibenz(a,h)anthracene fluoranthene fluorene ideno(1,2,3-cd)pyrene 3-methylcholanthrene 1-methylnaphthalene 2-methylnaphthalene naphthalene phenanthrene pyrene
w/data pack
Each 31618 31618-500
5-pk. 31618-510 31618-520
10-pk. 31718

aniline benzidine 4-chloroaniline 3,3'-dichlorobenzidine diphenylamine 2-nitroaniline 3-nitroaniline 4-nitroaniline N-nitrosodimethylamine N-nitrosodi-n-propylamine pyridine
w/data pack
Each 31625 31625-500
5-pk. 31625-510 31625-520
10-pk. 31725
w/data pack
Each 31619 31619-500
5-pk. 31619-510 31619-520
10-pk. 31719
w/data pack
Each 31622 31622-500
5-pk. 10-pk. 31622-510 31622-520 31722
CLP GPC Calibration Mix

Qualitative mixture useful for determining GPC dump/collect times. Data packs are not available. The compounds are dissolved in methylene chloride at the concentrations listed.
EPA CLPSemivolatiles Calibration Mixtures

04.1 SOW, 04.2 OSW
Restek chemists carefully reviewed the 04.2 Statement of Work and determined that the identical products listed in 04.1 will also be required for the 04.2 revision. The products listed here are a result of this work.
CLP GPC Calibration Mix

bis(2-ethylhexyl)phthalate corn oil methoxychlor perylene sulfur In methylene chloride, 1mL/ampul 10mg/mL 250 2.0 0.2 0.8
CLP 04.1 Phenols Calibration Mix

4-chloro-3-methylphenol 2-chlorophenol 4-nitrophenol 2,4-dichlorophenol 2,4-dimethylphenol 2,4-dinitrophenol 2-methyl-4,6-dinitrophenol 2-methylphenol 4-methylphenol 2-nitrophenol pentachlorophenol phenol 2,4,5-trichlorophenol 2,4,6-trichlorophenol
CLP OLM 04.1 SV Kit #1

31000: SV Screening Mix 31001:SV Tuning Mix 31493:CLP 04.1 BNA Surrogate Mix 31492:CLP 04.1 B/N Matrix Spike Mix 31005:Acid Matrix Spike Mix 31006:SV Internal Standard Mix 31494:CLP 04.1 Phenols Calibration Mix 31495:CLP 04.1 B/N MegaMix 31012:SV Calibration Mix #6 (pesticides) Contains 1mL each of these mixtures.
kit
1mL/ampul 5mL/ampul
Each 32019 Each 32023
5-pk. 32019-510 5-pk. 32023-510
10-pk. 32119 10-pk. 32123
Each 31494 w/data pack 31494-500
5-pk. 31494-510 31494-520
10-pk. 31594
Revised GPC Calibration Mix

bis(2-ethylhexyl)phthalate corn oil methoxychlor perylene sulfur In methylene chloride, 1mL/ampul 5mg/mL 250 1.0 0.2 0.8
Kit 31603
CLP 04.1 B/N MegaMix

Note: This product is provided as a two ampul set: CLP 04.1 B/N MegaMix Mix A

31494:CLP 04.1 Phenols Calibration Mix 31495:CLP 04.1 B/N MegaMix 31012:SV Calibration Mix #6 (pesticides) Contains 1mL each of these mixtures.
kit
1mL/ampul 5mL/ampul
Each 32041 Each 32042
5-pk. 32041-510 5-pk. 32042-510
10-pk. 32141 10-pk. 32142
tek Res ip T
CLP OLM 04.1, 04.2 Semivolatile Dilution

Benzaldehyde and atrazine will react quickly and directly with the methanol stabilizer used in most brands and grades of methylene chloride. This reaction will prevent you from obtaining stable, working-level calibration standards. Therefore, Restek has prepared the CLP OLM 04.1 Semivolatile B/N Mega- Mix from methylene chloride that is stabilized with amylene and is completely free of methanol. Restek strongly recommends screening the methylene chloride you use to dilute these mixtures to confirm that it is free of methanol.
acenaphthene acenaphthylene acetophenone anthracene atrazine benzo(a)anthracene benzaldehyde benzo(a)pyrene benzo(b)fluoranthene benzo(k)fluoranthene benzo(ghi)perylene 1,1'-biphenyl bis(2-chloroethoxy)methane hexachlorocyclopentadiene bis(2-chloroethyl)ether bis-(2-chloroisopropyl)ether bis(2-ethylhexyl)phthalate 4-bromophenyl phenyl ether butyl benzyl phthalate caprolactam carbazole 2-chloronaphthalene 4-chlorophenyl phenyl ether chrysene di-n-butyl phthalate
di-n-octyl phthalate dibenz(a,h)anthracene dibenzofuran 3,3'-dichlorobenzidine diethyl phthalate dimethyl phthalate 2,4-dinitrotoluene 2,6-dinitrotoluene fluoranthene fluorene hexachlorobenzene hexachlorobutadiene hexachloroethane ideno(1,2,3-cd)pyrene isophorone 2-methylnaphthalene naphthalene nitrobenzene n-nitrosodi-n-propylamine n-nitrosodiphenylamine phenanthrene pyrene
Kit 31604

31494:CLP 04.1 Phenols Calibration Mix 31495:CLP 04.1 B/N MegaMix Contains 1mL each of these mixtures.
kit
Kit 31605
1,000g/mL each in methylene chloride/benzene (75:25)
CLP 04.1 B/N MegaMix Mix B

4-chloroaniline 2-nitroaniline 3-nitroaniline 4-nitroaniline
1,000g/mL each in methylene chloride
w/data pack
Each 31495 31495-500
5-pk. 10-pk. 31495-510 31495-520 31595
27
EPA CLPSemivolatiles Calibration Mixtures and Kits

3/90 and 4/89 SOW
SV Calibration Mix #1
benzyl alcohol 4-chloroaniline 2-nitroaniline 3-nitroaniline 4-nitroaniline
acenaphthene acenaphthylene anthracene benzo(a)anthracene benzo(a)pyrene benzo(b)fluoranthene benzo(k)fluoranthene benzo(ghi)perylene chrysene dibenzo(a,h)anthracene fluoranthene fluorene indeno(1,2,3-cd)pyrene naphthalene phenanthrene pyrene
CLP Semivolatile Calibration Kit #1

(with pesticides)
31007: SV Calibration Mix #1 (anilines) 31008: SV Calibration Mix #2 (phenols) 31009: SV Calibration Mix #3 (base neutrals) 31010: SV Calibration Mix #4 (base neutrals) 31011: SV Calibration Mix #5 (PAHs) 31012: SV Calibration Mix #6 (pesticides) 31013: SV Calibration Mix #7 (dichlorobenzenes) 31026: 3,3'-dichlorobenzidine Contains 1mL each of these mixtures.
kit
2,000g/mL each in CH2Cl2, 1mL/ampul
w/data pack
Each 31007 31007-500
5-pk. 31007-510 31007-520
10-pk. 31107
benzoic acid 4-chloro-3-methylphenol 2-chlorophenol 2,4-dichlorophenol 2,4-dimethylphenol 2,4-dinitrophenol 2-methyl-4,6-dinitrophenol 2-methylphenol 4-methylphenol 2-nitrophenol 4-nitrophenol pentachlorophenol phenol 2,4,5-trichlorophenol 2,4,6-trichlorophenol
w/data pack
Each 31011 31011-500
5-pk. 31011-510 31011-520
10-pk. 31111
Kit 31461
aldrin -BHC -BHC -BHC -BHC (lindane) 4,4'-DDD 4,4'-DDE 4,4'-DDT dieldrin endosulfan I endosulfan II endosulfan sulfate endrin endrin aldehyde endrin ketone heptachlor heptachlor epoxide (B) methoxychlor
CLP Semivolatile Calibration Kit #2

(without pesticides)
31007: SV Calibration Mix #1 (anilines) 31008: SV Calibration Mix #2 (phenols) 31009: SV Calibration Mix #3 (base neutrals) 31010: SV Calibration Mix #4 (base neutrals) 31011: SV Calibration Mix #5 (PAHs) 31013: SV Calibration Mix #7 (dichlorobenzenes) 31026: 3,3'-dichlorobenzidine Contains 1mL each of these mixtures.
kit
w/data pack
Each 31008 31008-500
5-pk. 31008-510 31008-520
10-pk. 31108
bis(2-chloroethoxy)methane bis(2-chloroethyl)ether bis(2-chloroisopropyl)ether bis(2-ethylhexyl)phthalate 4-bromophenyl phenyl ether butyl benzyl phthalate 2-chloronaphthalene 4-chlorophenyl phenyl ether dimethyl phthalate di-n-butyl phthalate di-n-octyl phthalate N-nitrosodimethylamine N-nitroso-di-n-propylamine N-nitrosodiphenylamine
2,000g/mL each in toluene/hexane (1:1), 1mL/ampul
w/data pack
Each 31012 31012-500
5-pk. 31012-510 31012-520
10-pk. 31112
Kit 31462
1,2-dichlorobenzene 1,3-dichlorobenzene 1,4-dichlorobenzene 2,000g/mL each in CH2Cl2, 1mL/ampul
Semivolatile Calibration Kit #3

(with benzidine)
31007: SV Calibration Mix #1 (anilines) 31008: SV Calibration Mix #2 (phenols) 31009: SV Calibration Mix #3 (base neutrals) 31010: SV Calibration Mix #4 (base neutrals) 31011: SV Calibration Mix #5 (PAHs) 31013: SV Calibration Mix #7 (dichlorobenzenes) 31030: 605 Benzidines Calibration Mix (benzidine & 3,3'-dichlorobenzidine) Contains 1mL each of these mixtures.
kit
w/data pack
Each 31009 31009-500
5-pk. 31009-510 31009-520
10-pk. 31109
carbazolehexachlorocyclopentadiene dibenzofuran hexachloroethane diethyl phthalate isophorone 2,4-dinitrotoluene 2-methylnaphthalene 2,6-dinitrotoluene nitrobenzene hexachlorobenzene 1,2,4-trichlorobenzene hexachlorobutadiene 2,000g/mL each in CH2Cl2, 1mL/ampul
w/data pack
Each 31013 31013-500
5-pk. 31013-510 31013-520
10-pk. 31113
3,3'-Dichlorobenzidine
2,000g/mL each in methanol, 1mL/ampul
Kit 31463 10-pk. 31126
w/data pack
Each 31026 31026-500
5-pk. 31026-510 31026-520
Semivolatile Organics Kit (3/90 SOW)

31000: SV Screening Mix 31001: SV Tuning Compound 31002: B/N Surrogate Std. Mix (3/90 SOW) 31003: Acid Surrogate Std. Mix (3/90 SOW) 31004: B/N Matrix Spike Mix 31005: Acid Matrix Spike Mix 31006: SV Internal Standard Mix 31007: SV Calibration Mix #1 31008: SV Calibration Mix #2 31009: SV Calibration Mix #3 31010: SV Calibration Mix #4 31011: SV Calibration Mix #5 31012: SV Calibration Mix #6 31013: SV Calibration Mix #7 31026: 3,3'-dichlorobenzidine Contains 1mL each of these mixtures.
kit
w/data pack
Each 31010 31010-500
5-pk. 31010-510 31010-520
10-pk. 31110
Kit 31051
Kit w/Data Pack 31151
PATENTS & TRADEMARKS Restek patents and trademarks are the property of Restek Corporation. Other trademarks appearing in Restek literature or on its website are the property of their respective owners.
Lit. Cat.# 59411A

202 Restek Corporation.
Restek U.S. 110 Benner Circle Bellefonte, PA 16823 814-353-1300 800-356-1688 fax: 814-353-1309 www.restek.com Restek France phone: +33 (0)1 60 78 32 10 fax: +33 (0)1 60 78 70 90 e-mail: restek@restekfrance.fr Restek GmbH phone: +49 (0)6172 2797 0 fax: +49 (0)6172 2797 77 e-mail: info@restekgmbh.de Restek Ireland phone: +44 (0)2890 814576 fax: +44 (0)2890 814576 e-mail: restekeurope@aol.com Restek Japan phone: +81 (3)6459 0025 fax: +81 (3)6459 0025 e-mail: ryosei.kanaguchi@restek.com Thames Restek U.K. LTD phone: +44 (0)1494 563377 fax: +44 (0)1494 564990 e-mail: sales@thamesrestek.co.uk

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Guide to Preparing and Analyzing Semivolatile Organic Compounds

(814-353-1300, ext. 4) or email us at

support@restek.com (U.S.) intltechsupp@restek.com

Resteks Customer Commitment

Gel Permeation Chromatography

Analysis Calibration Standards

Injection Port Configuration

Figure 1. Optimizing splitless hold time.

component area (thousands)

45 60 75 hold time (sec.)

59,60 8,9 50,51

10,11,12 32 4,5,6 2,3 1 62 63 65 64 66 70 67 71 72 73 74 75 77 78 68,69

Peak List for Figures 6 & 7

10,11,12 28 5,6 2,3 7 4 26 23,24 13,14 15,16 22 18 25 17 19 20 21 29 30 35 31 34 33 39 40 48 46 45 54 52 53 55 58 49 57 32 36 37 41 44 47 56 60 61 62 63

15.0 15.5 16.0 16.5 69,70 67 68 71

17.0 17.5 18.0 18.5

19.0 19.5 20.0 20.5 min.

13,14 15,16 27,28 32 4,5,6 8,9 2,3 7 18 17 23,24 26 22 25 30 29 31 35 34 33 40 39 48 36 37 41 47 60 61 49 62 52,53 55 54 56 57 63 44 42,43

Peak list on page 13

Det. type: Transfer line temp.: Scan range: Ionization: Mode:

responce (area counts)

Rtx-5MS and Rtx-5Sil MS Columns

60-Meter 12611 12626 12641 12612 12627 12642

Fused Silica (Crossbond 5% diphenyl - 95% dimethyl polysiloxane) Stable to 360C

Innovative Integra-Guard Columns

Intermediate-Polarity Deactivated Guard Columns

ID*/OD & Length (mm)

Similar to 25-pk. Agilent part #

Cyclo Double Gooseneck (2mm)

Cyclo Double Gooseneck (4mm)

Drilled Uniliner (4mm)

Siltek Drilled Uniliner (4mm)

For Varian GCs

ID**/OD & Length (mm)

cat.# 5-pk. 25-pk.

Similar to Varian Part #

Cyclo Double Gooseneck

1078/1079 Liners for Varian GCs

ID**/OD & length (mm)

cat.# 5-pk. 25-pk.

Similar to Varian Part #

*Nominal ID at syringe needle expulsion point.

ID**/OD & Length (mm)

cat.# 5-pk. 25-pk.

Similar to Shimadzu Part #

94mm Double Gooseneck

94mm Single Gooseneck

For PerkinElmer GCs

ID**/OD & Length (mm)

cat.# 5-pk. 25-pk.

Auto SYS Double Gooseneck

Auto SYS Cyclo Double Gooseneck

Auto SYS XL Split/Splitless

For Thermo Orion GCs

ID**/OD & Length (mm)

cat.# 5-pk. 25-pk.

Splitless (4mm ID)

Splitless Liners for 8000 & TRACE Series GCs