Analysis of Exempt Paint Solvents by Gas Chromatography Using Solid-Phase Microextraction

Rosemarie R, Bodrian, Albert C, Censullo, Dane R, Jones, Mark J, Rashkin, a n d Max T, Wills*Golden Gate Society for Coatings Technology Technical Commibee

Acetone, methyl acetate, and parachlorobenzotrifluoride (PCETF or OxsoI | 100) have been exempted as VOC solvents by the U.S. Environmental Protection Agency. ~n measuring coating VOC content, separate methods for determining exempt solvents are required. One such method utilizes solid-phase microextraction ( S PME ) to sample the headspace of soIvent-based coatings to which the surrogates acetone d6, methyl acetate d3, and~or metachIorobenzotrifluoride have been added. The sampled exempt coating solvents are thermally desorbed and analyzed using gas chromatography with flame ionization or mass spectral detection. The SPME headspace method has also been used to analyze M E K butyl acetate, tort-butyl acetate, toluene, and xylene in solventborrze coatings, and alcohols in waterborne systems. This paper presents the results obtained for acetone and toluene in a large number of aerosoI paints. Additionally, the results from a round rotn'n study for acetone, methyl acetate, and parachlorobenzotrifluoride in commercial solvent based coatings are reported.

Acetone, methyl acetate, and parachlorobenzotrifluoride (PCBTF) have been exe m p t e d as volatile organic compound (VOC) coatings solvents and are not in cluded in the measurement of coating VOC content. A separate method for the determination of exempt solvents must therefore be carried out w h e n VOC is determined b y EPA Method 241 (ASTM Practice D 39602). As of December 4,1997, the EPA has received petitions requesting V 9 exempt status for tert-butyl acetate, 3 dimethyl succinate and dimethyl glutarate, 4 1 bromopropane, s and other solvents normally not used in coatings. As each new solvent is approved and finds use in coatings, the VOC determination becomes ever more complex since each of the exempt solvents requires a unique method of measurement. Gas chromatography appears to be the only method currently available for carrying out the determination of individual sol vents. It has been shown that the speciated and total VOC content of waterborne paints m a y be determined b y direct in jection into a gas chromatograph. 6 The results obtained were generally good, and the method used is particularly effective for analyzing low V9 content coatings. Direct gas chromatography of whole paints has also been used to study
*Department of Chemidw. California Polytechnic State University, San Luis Obispo, CA 93407

both solventborne 7 and waterborne coat ings to obtain information on hazardous air pollutants (HAPs) using EPA Method 311. 8 The results obtained in an ASTM interlaboratory study of EPA Method 311 indicated that the precision was generally poor. 9 The direct quantitative gas chromatographic analysis of volatile solvents in coatings is often difficult due to the relatively complex nature of most coatings matrixes. The n o n v o l a t i l e c o r n ponents present in m a n y coatings often make it difficult to obtain homogeneous solutions/dispersions with diluting solvents. W h e n coathGs solutions/dispersions are injected onto a gas chromatographic column, decomposition of the n o n v o l a t i l e components may occur in a heated injection port generally main tained above 240~ giving unwanted chromatographic signals and possibly resulting in fouling of expensive ana lyrical systems and colun~s. Analytical precision is often compromised and time is often wasted in restoring analysis capabilities. For solventborne systems we have developed a unique distillation method for quantitatively s e p a r a t i n g volatile components from n o n v o l a t i l e compo n e n t s ) ~ The method is a modification of ASTM Method D 3272, "Vacuum Distil lation of Solvents from Solvent-Reducible Paints for Analysis. "~ In the modification, a one- or t w o - g r a m sample of the coating is mixed with 5 mL of dioctyl phthalate (di-2-ethylhexyl phthalate) and two grams of tetradecane. The mixture

is then v a c u u m distilled, and the distil late is trapped in liquid nitrogen. The n o n v o l a t i l e dioctyl phthalate serves as a dispersion m e d i u m for the coating, and the tetradecane serves as a chase solvent for the coating volatiles durh G the distillation. Since most coatings contain volatiles with boilhG poh~ts below that of tetradecane, distillation of a portion of the tetradecane allows quantitative transfer of the coatings volatiles to the liquid nitrogen trap. In addition, the t e r n perature during v a c u u m distillation is not allowed to exceed 110~ thus minimizh G potential non-volatile decomposition and approximating the same temperature used during determination of the coating volatile content b y ASTM Method D 2369.12 The distillate is gas chromatographed on both a 100 m • 0.25 m m polydimethylsiloxane and 60 m x 0.25 m m Carbowax TM capillary column and quantitatively speciated after deterruination of relative response factors for each analyte present h~ the sample. After determination of total volatile content b y ASTM D 2369, absolute amounts of each analyte m a y be determined. A1 ternatively, an internal standard can eas ily be incorporated prior to the v a c u u m distillation and then used to determine absolute amounts of each analyte. This method has been used to analyze the liquid coath G portion of more than 40 diverse solventborne aerosol pah~ts. 13 A method was needed to validate the result s obtained b y v a c u u m distillation / gas chromatography and since a large

Vol. 72, No. 900, January 2000


both flame ionization detection (SPME/GC/FID) and mass spectral de tection (SPME/GC/MS) were used to measure analyte concentrations. a sample of paint is weighed into a septum-capped vial c o n t a i n i n g a d i s p e r s i o n m e d i u m of dicoctyl phthalate (solventborne paint) or salt solution (waterborne paint). One of the most significant charac teristics of the headspace SPME method is that the amount of each analyte ex t r a d e d b y the fiber is not proportional to the amount of that analyte present in the headspace. methyl ethyl ketone.) or equiva lent.5 btln fihn thickness. methyl ac etate. methyl p r o p y l ketone. and methyl amyl ketone dispersed in dioctyl phthalate.r o b i n study.H e l i u m Flow Rate--1. Gas4ight syringe s a m pling gave an area ra tio of 100:49:8 a n d SPME sampling gave an a r e a r a t i o of 100:112:190. i n c l u d i n g p a r a c h l o r o benzotrifluoride (PCBTF or Oxsol | 100).1 FID Instrument Conditions: D e t e c t o ~ F l a m e ionization Column 60 m x 0. except parachlorobenzotri-fluoride. and butyl acetate. as well as their boiling points. 70 Journal Coatings Technology of . are preferentially ab sorbed onto an SPME f i b e r r e l a t i v e to a much higher headspace concentration of a low molecular weight material. Dep e n d i n g on the analyte of interest.3.25 ram DB Wax (J&W Scientific Co.--Integrator--Any electronic integrator that can accurately quantify a gas chromatographic p e a k area is an acceptable integrator. The SPME method was found to be simple to use and gave very precise results. ethyl acetate. and 2 propanol. Surrogates were chosen based on the following criteria: (1) The boiling point is nearly the same as the corresponding analyte. Tile same procedure m a y be used for other analytes in solventborne paints by incorporating the appropriate internal standard as indicated in Table 1. W h e n s a m p l i n g the h e a d space of a paint. Carrier G a s . 1. a n d PCBTF since these have been exempted as VOCs b y the U.1 Manual SPME holder fitted with a C a r b o w a x / D i v i n y l b e n z ene ( C W / DVB) fiber assembly. ethanol. In using this method for deter mining paint solvents. 65 ~tm film thickness. (3) GC peak separation f r o m t h e corresponding analyte occurs. Larger molecules are adsorbed more strongly to the fiber resulting in preferential adsorption to the fiber.2. This effect is illustrated in Fig ure 2 for equal masses of acetone. We have e x t e n d e d the SPME m e t h o d for the analysis of other common solvents found in c o a t i n g s . A round robin SPME study was conducted for the solv e n t s acetone. but i s o t h e r m a l o p e r a t i o n s m a y be utilized.--A 0. A n equilibrium is established between the amount of analyte in the headspace and the amount of analyte adsorbed on the fiber. The headspace above the solution is sampled with an SPME fiber a n d then d e s o r b e d in a heated GC inlet onto a capillary column. high boiling solvents.75 m m inlet liner should be placed in the injection port. and tert-butyl acetate. Tile headspace of this ketone mixture was sampled using both a gas tight sy ringe and an SPME syringe and injected/ desorbed onto a gas chromatograph. APPARATUS AND REAGENTS: number of the samples contained acetone a n d / o r toluene. Environmental Protection A g e n c y . the surrogate was a deuterated analog of the analyte. FID Detec tion: A n y c a p i l l a r y gas c h r o m a t o g r a p h e q u i p p e d w i t h a flame ioni z a t i o n d e t e c t o r m a y be u s e d . The analytes and corresponding su> rogates studied. even when present in very low concentration in the headspace. partially crosslinked (Supelco) was used.S. tetiary b u t y l acetate. (2) The structure is similar to that of the corresponding analyte. EXPERIMENTAL Tile following is a detailed procedure for the analysis of acetone. 1. In the r o m l d . A d i a g r a m for the experimental extraction setup is shown in Figure 1.2. and parachlorobenzotrifluoride (PCBTF) in solventbome coatings using either S P M E / G C / f l a m e ionization de tection or S P M E / G C / m a s s spectral de tection. methyl isobutyl ketone. Tile same effect was observed for a mixture of methyl acetate. methanol. coated with an appropriate adsorbent. Ontario. were 100:32:11:5:1 w h e n sampled b y gas-tight syringe and 100:104:118:101:82 w h e n sampled b y SPME. A fiber coated with a 65 btm film of Carbowax-divinyl-benzene was used for all analytes studied.0 mL p e r rain (20 cm p e r sec) Split Rarity--200 to 1 Fiber Desorption T i m e ~ to 6 sec Temperatures. xylene.2. Temperature programming capability is desirable. ~ Inlet 260 ~ Detector270 ~ Initial--35 ~ for 12 rain Rate 1--30 ~ per rain to 100 ~ hold 10 rain Rate 2--30 ~ per rain to 240 ~ hold 2 rain 1. me thyl ethyl ketone. m e t h y l acetate. these analytes were de termined separately b y solid phase mi cro e x t r a c t i o n (SPME).2 Gas C h r o m a t o g r a p h . are shown in TabIe 1. which is attached to a modified GC sy ringe. The SPME fiber consists of a section of fused silca. 0. butyl acetate. as the mo lecular weight increases. and (4) It is not a component of the paint sample being analyzed.2.Golden Gate Society Technical Committee solution onto a coated fiber. an appropriate surrogate is weighed into the vial and the mixture is agitated and allowed to equilibrate.. 1. butyl ac etate. The resulting relative peak areas. Canada and involves the extraction of analytes from a liquid headspace or from an aqueous 1. In all cases. SPME w a s initially d e v e l o p e d b y Janusz pawliszyn 14-16 at the University of Waterloo.

..... 55.. 1.0 mL per rain (20 cm per sec) Split Ratio 200 to 1 Fiber Desorption T i m e ~ to 6 sec Temperature. 82 1.... A c e t o n e ........11 gin film thickness Carrier Gas---Helium Flow Rate--1....3.. The detector must be capable of measuring in the selected ion monitoring (SIM) mode at dwell times of 100 rail liseconds or less.. 2....0 ... the propellant front each was transferred to a gas sampling bag..... methyl acetate d3.. 2...... Toluene..p.... The paint should drop directly into the dicoctyl phthalate... The volatile portion was gas chromatographed to give the speci ated profile of the volatile compounds 71 Vol.. 1 ~ e i g h 0.....20 m m H P 6 (Hewlett Packard Co... 0....5 Sample the headspace with the SPME fiber for 60 sec....1--Place 6 mL dioctyl phthalate into a 22 or 40 mL vial and seal with a septurn cap....... Methyl acetate. 142 Methanol-d3.. retention time in minutes.. 74...............34.1 mg into the vial... Galactic Industries) for measuring peak areas is advantageous in some instances... 98 ... 64... Methyl ethyl ketone.2--Determine which. and 180 Dwell Time 100 milliseconds or less Solvent D e l a y 0 . 4..75 m m inlet liner should be placed At the injection port.3 Gas Chromatograph....2...... 3 . b. Weigh the amounts of PCBTF and MCBTF to 0.A n a l y s i s of E x e m p t Paint Solvents 1..... into a septum-capped vial contafftff G 6 mL dioctyl phthalate........ m / e .........3... 82...... 7 2 .........5 ... 2-Propanol. 77.... methyl acetate -d3........... PCBTF....9% isotopic p u r i t y . ~ Inlet 260 ~ Detector--280 ~ Initial~40~ for 2 rain Rate 1--10 ~ per rain to 90~ hold i rain Rate 2---40~ per rain to 240~ hold 1 rain 1..........1.. 180.. 2.......1.. 77. methyl acetate.. The n u m e r i c a l values should agree within 1% of each other... technical grade..... methyl acetate. 1. Surrogate.......... 137-138 Methyl dO a c e t a t e d3.. correspond ing to the analytes found in 3... 110 Elhylbenzene d l 0 ....p. 0..... 99.. 101 Methyl valerate.....3--The instrument should have a software data systemto allow extraction and integration of the SIM ions.............. ~ A c e t o n e ... 180.34......3... and the remaining liquid coating was distilled u n d e r v a c u u m to separate the volatiles and n o n volatiles. BuM acetate.~ MI and %Analyte AI * MA AA~MI*IO0 AI * RF 9 MC 2. acetone.9. 1...d l G 135 o Xylene dlO..6 p ...........26...... MCBTF.....8 If using the GC/FID procedure............7...5 t o 1.) or equivalent..... 58.26. 57.. 99.....1 rag.......4 Remove the cap and wipe the sep turn to remove solvent from the in ner surface and reseal immediately...3 to 2... of the three exempt solvents are present in the paint sample and if interfering peaks are present at the retention times corresponding to the retention times of the internal standards....... and PCBTF accordffG to the equation given in section 3.... or replace the septum with a n e w one.. 78 2-Propanol-d7...9% isotopic purity.. 1.........3--Manually shake the vial for 15 sec to mix the content and then let the vial stand at roomtemperature for30 rain...7 .....5 Repeat the procedure given in sec tion 3..9--If usffG the G C / M S procedure.0 Methyl h i m e t h y l a c e t a t e .... Mass Selec rive (MS) Detection: A n y capillary gas chromatograph equipped with a mass selective detector may be used.5 2 B u l a n o n e 1. 2.4.2--Using dedicated 250 gL syringes....... 74.. 2. acetone d6...... Methanol.7--Clean the fiber by placffG it in the GC injection port for 15 sec after the analytes of interest have p a s s e d through the capillary column. A duplicate injection of the same sample should give relative peak areas which agree within one percent of each other. Table I --Analytes and Corresponding Surrogates Analyte.. 2..... tert-Bulyl a c e t a t e ....X y l e n e .... b. RESULTS Aerosol Coatings 3 .... 1... 56.... 64....3 d5 3-Chlorobenzotrifluoride. Curve fitting software (GRAMS/32.. 2..3.. 0 rain Column 25 m x 0. In the course of a study of more than 40 diverse solventbome aerosol paints... 57. 4 ~ a l c u l a t e analyte concentrations according to the following equations: RFAA..... 4....... 97%....0 g of well mixed paint into a septum capped vial con raining 6 mL of dioctyl phthalate us ing a disposable 1 mL syringe. ~ .... Parachlorobenzotrifluoride.....90. 65.......10 Calculate response factors (RF) for acetone..4 . Carry out the same procedure as described in 2.84......... 64.. Carry out the same procedures as described in 2........ if any. 110. 128 Toluene-d8... Repeat the proce dure by adding approximately 150 mg each of acetone.... PREPARATION OF STANDARDS: 2.........3.2 or 1...d 6 .. parachlorobenz otrifluoride (PCBTF).1 rag...6 ... Ethanol.4 Ethanol d5.4~Required reagents include: Acetone -d6.. 124 126 ....2--A 0.. measure the peak areas of the three analytes and three standards by inte gration.1 MS Instrument Conditions: Detector--Electron ionization or mass selective Detection Mode--SIM of ions m / e 58.. Excess solvent should be wiped from the syringe needle prior to piercing the septum......... measure the peak areas for the extracted ions as follows: analyte... 137 144 ........0 g of paint sample and 100 mg of each of the internal standards......... 136-138 ...5 to 1.. 78 .1 rag. 134.3 u s i n g p a i n t and internal stan dard amounts such that the relative peak areas of the analyte and its fitternal standard chromatographic peak areas are approximately the same size. weigh approximately 100 mg each of parachlorobenzotrifluoride and meta chlorobenzotrifluoride to 0... A n y solvent adherh G to the outside of the septurn cap after making the transfer should be w i p e d off with tissue.. No. January 2 0 0 0 .. 80 .......6--Desorb the SPME fiber for 5 to 6 sec in the injection port of the gas chromatograph using either the conditions described in 1.. 3 ~ e i g h to 0. 99+% was obtained from the Occidental Chemical Cor poration and has the trade n a m e Oxsol ~ 100. 3 . 2..... acetone d6. 3.. Xylene............... me thyl acetate and methyl acetate d3 and weigh each component to 0....3 to 2.... PAINT ANALYSIS: where RF = Response factor AA = Area of analyte MI = Mass of internal standard AI Area of internal standard MA Mass of analyte MC Mass of coating 3. 9 0 0 .. 1....... metachlorobenzotrifluoride (MCBTF)..

SPME 28. 34.........93 56. 11.... 28......40 0........ Based on these results. All of the laboratories used the SPME sampling technique.. 4 3 . 0.. and two of the laboratories used MS detection to measure analyte amounts.85 ... 21..00 0...97 0...54 43....08 .... added methyl acetate.. reproducibility standard deviations (SR)....16 0.17 ......18 -1....01 0...... 3 6 ............. therefore.70 13.62 2. Of 18 samples which con rained acetone.....97 0....47 ......41 0...98 0.92 ....87 42.09 43.. A comparison of these two entirely different methods indicate that both methods gave very good results (Table 2)... and the appro priate internal standards is shown in for each coating..47 -- % Acelone Distillation 27.39 0....41 38.... This should equal exactly 1 00 if the two methods produced identical results 72 Journal of Coatings Technology ...97 0. repeatability at the 95% confidence limit (r)....96 13.....04 1. .. 4 2 ... 35..........65 -40. ... 3 7 ....49 ...... 5 7 .IX] ....03 0...... 8 7 .. 6 3 .12 0....73 55. Average values..48 ...33 54... Error= 1.. prepared by adding k n o w n a m o u n t s of methyl acetate to different cellulose nitrate lacquers.02 -1......99 1.28 -43.. 4 8 ....40 -49..........73 SPMI:/DJsl b 0.46 .99 3..52%...... 3 4 . A round robin was conducted involv h~g five laboratories......43 29.57 13..03 1. % Toluene Distillation 36.. SPME/GC/FID was used to validate the results obtained for acetone a n d / o r toluene in 23 of these aerosol coatings......92 .........47 -38.28 -40.62 40.....95 0..82 40...66 -......19 36.....03 1....... Two of the six coat hGs were parts of a two-component pigmented primer which were analyzed as two separate coatings....11 0.. 11...68 ...24 48....12 72.......Golden Gate Society Technical Committee FID to measure analyte amounts...... ... the average difference b e t w e e n the two methods was 1.....71 -0... the average difference between the two methods was 0.62 -- Error= 1.... 40..97 -1. .... Three of the laboratories used Table 2--Comparison of SPME and DistillalJon Results for Acetone and Toluene Sample 2 7 ..32 0...06 37..97 ...60 1... 3 9 . 27........71 56.85 39.......51 54.... Four of the coat ings contained acetone and two of the same four coatings contained both ac etone and parachlorobenzotrifluoride..98 1 . 4 5 .18 -38..87 -1... 3 5 ...96 0....83 51.....96 0..... Six commercial solventborne coat ings were analyzed........ Round-Robin Analysis of C o a t i n g s Containing E x e m p t Solvents Figure 3...06 -...... 21.43 ....27 68...........82 30.... it was believed that the SPME/GC method could serve as a simple and clean method for q u a n t i f y i n g exempt and other individual solvents in coatings.00 39. Four of the six coatings were nitrocellu lose lacquers obtained from two differ ent manufacturers.... A typical FID chromatogram of a nitrocellulose lacquer containing acetone.55 11..87 38..99 1.....02 SPME 34...... 41 .98 1....99 1........ A v g ........ 70. (b) Retie of composition as determined by SPME relative to dis/illotion procedure.04 0.36 69....28 41.52 SPME/Distb 1...... 42. and reproducibility at the 95% confidence limit (R) are given for each coating and exempt solvent in Tables 3 and 4.. 3 8 ... 67.....01 0.. 4 9 .84 56.19 1......02 1.28 53.....23 49... Of 10 samples which contained toluene. .... 5 0 .......16%.01 -1..63 -43....68 -50....... Precision data was calculated sepa rarely for the three laboratories using FID and the two laboratories ush G MS detection and also for the combination of FID and MS detection.60 ..47 54... ...79 .... The laboratories participathG in the rotund-robin were experienced in both gas chromatograp h y and SPME methodology..75 ........ repeatability standard deviations (Sr).. ..05 0......84 1.97 (a) Difference between distillation and SPME result............ 0.71 52........58 1............. 0..68 .............66 13..... 6 6 ....99 1. 1..... 51 ......... 4 4 .53 71.... 0. 0. 6 7 .96 .. .. added PCBTF.02 0..38 43.41 1.... 2 9 ....... 6 4 .15 43.... Coatings contah~hG methyl acetate were not yet available in the marketplace w h e n this rom~d-robh~ was carried out and were.....39 9.

A v e r a g e % (FID + MS) ..54 1.18% absolute for acetone.. In an alternate procedure..66 1.. and 0..29 1..99 0...48 0..49 0.. Reproducibilily standard deviation Repeatability..... 95% confidence limit........31 0.16% absolute at 19 degrees of free dora for methyl acetate........47% absolute for parachlorobenzotrifluoride.....35 0...41 0...6 28..61 1............... The boil ing points of these two solvents differ by only three degrees Celsius and they are structurally similar so they would be expected to adsorb onto the SPME fiber at about the same rate.55 0..87 1........94% absolute for acetone.... A v e r a g e % (MS) . The 95% confi dence limit for the difference between two such averages is 1...29 0....9 47...39 0.........17 For Laboratory Precision (within laboratory.. Since the modified v a c u u m distillation procedure is relatively simple to carry out..........9 0...52 0..... R (FID) ....0 0.............28 0........ respectively....... If these oxygenated solvents are present in a solventborne coating...41 0. has been estimated to be 0......30 0....30 0..... we recommend that it be between days variability.. 0.. SR (MS) .............83 1..15 0..52 0. Sr (FID + MS) ..... 1.8 0.49 0...11 0....58 0.....0 11.... 1.3 88... The pure ester was obtained by extracting with p cymene..19 0.................69% absolute at 39 de grees of freedom for acetone......1 16..... water is used as a dispersion medium............38 0...46 0.38 0...53 0.......69 0......54 0... 9 0 0 ....22 0...........14 1..................... A major advantage using SPME is that non volatile coating constituents are not in troduced into the chromatographic sys tern.......... The addition of solid s o d i u m chloride to the water dispersion med i u m increases the analyte concentra tion in the headspace and should be used w h e n the analytes are present in low concentration.....20 0. Filtration followed by two simple distillations gave isotopi cally pure methyl acetate-d3......... Table 3--Precision D a t a for A c e t o n e Material Sample A v e r a g e % (FID) .. formerly called re peatabiIity) the standard deviation of re sults (each of the average of duplicates).43 0....46 1..55 0.8 16............ Toluene.10 0. has been estimated to be 0...... The standard deviation for Reproducibility (MuItiIaboratory) of results (each the average of duplicates). If they are present in a waterborne coating...............34 0...5 0.....62 1. and 0.36 1.0 12.....25 0......28 0...70% absolute for me thyl acetate..3 47..21 0...83 Repeate bility standard deviation...22 0...75 0. as surrogates. Table 4--Precision D a t a for Parachlorobenzolfifluoride a n d Methyl A c e t a t e Malerial Parachlorobenzotrifluoride Melhyl A c e l a t e I: Sample A v e r a g e % (FID) ..32 0.....19 0...55 B F 12..17 0. Synthesis of Methyl Acetate-d3 SUMMARY We highly recommend the S P M E / G C / FID or S P M E / G C / M S method for the analysis of selected analytes in coatings....... SF SR r R 1.....19 0........ and 0..1... SPME Analysis of Other Analytes The deuterated surrogate methyl acetate-d3 was synthesized from acetic acid d3 a n d excess m e t h a n o l b o r o n trifluoride complex..46% absolute for methyl acetate......................53 Repeatability standard deviation Reproducibility standard deviation........15 0....82 2......... SR (MS) .....53% ab solute at 19 degrees of f r e e d o m for parachlorobenzotrifluoride..49 0........55 0.. Sr SR r R 1. Sr (FIE)) . A v e r a g e % (MS) .42 21. R (FID + MS) .....27 0....62 1.. R (FID) .......65 0......... Sr (FIE)) ...0 0..........61 0.0 0.1 0..... R (FID + MS) ....58 1.. 7 2 ..58 0..... ethylbenzene..1 10.42% absolute at 39 degrees of freedom for acetone..63 0........... r (MS) . SR (FID) ..17 0.....99 0.. Sr (MS) ..59 0...76 0..Analysis of Exempt Paint Solvents The results were analyzed for precision using ASTM Practice E 180-94..6 21... ~ Methanol and ethanol may be analyzed in the same m a n n e r using methanol d3 and ethanol d5 as surrogates........ SR (FID + MS) ... A v e r a g e % (FID + MS) ...1....61 29.... 95% confidence limit..........34 0. and distillation to obtain the pure deuterated surrogate.... R (MS) .......63 10.0 0.........1 12.05 1...3 d5 as an i n t e r n a l standard...... SR (FID) .94 1.93 46... Repeatability.... A 16. Butyl acetate may be analyzed with methyl valerate as an internal standard..45 0....69 0...... We have p r e v i o u s l y reported the S P M E / G C analysis for 2-propanol........78 r (FID) . Reproducibility. 0... obtained by the same analyst on different days... The method gives very good precision and is relatively simple to perform... For the analysis of all the volatile components in a solventborne coating system....56 r (MS + FIE)) . p-xylene-dl0 or o-xylene-dl0.. 1.......95 0..4 27... R (MS) ......54 0.26 2.....22 0.25% absolute at 19 degrees of freedom for methyl acetate.......... Sr (FID + MS) .. 95% confidence limit Reproducibility..... 0. washing the extract with small quanti ties of water to remove excess methanol..... The 95% confidence limit for the difference between two such averages is 1.1 28...05 B C D r (FID) ..54 0.........77 1... dioctyl phthalate is used as the dispersion medium.. ethylbenzenedl0........... Methyl ethyl ketone may be analyzed with 2 b u t a n o n e 1....88 1..51 1. and 0.0 28. r (MS) .. SR (FID + MS) ... a distillation/ GC method as described earlier is rec ommended....10 1........53 89.....0 21.....49 0......................38 1... 95% confidence limit Vol. J a n u a r y 2 0 0 0 73 ........... which allows for continuous" clean" operation of the system....... r (MS + FIE)) .... and the three isomeric xylenes may be ana lyzed using toluene-d8.35% absolute at 19 degrees of freedom for parachlorobenzotrifluoride.57 0....... Acetone A 28..3......28 0. Sr (MS) ...83 For tert-butyl acetate the surrogate methyl trimethylacetate (methyl pivalate) gave excellent results... N o ....97% absolute for parachlorobenzotrifluoride. a mixture of two moles of acetic acid-d3 and one mole of methanol were stirred with Nafion| pellets and anhy drous m a g n e s i u m sulfate for two weeks at room temperature..7 89..

and Jones.01.. John Phillips. 569A (December 1994). Pawliszyn.R. Z. American Society for Testing and Materials..A. U. PA. Supelco. Cellulose C o m p a n y for p r o v i d i n g samples for the r o u n d robin study. EPA on5/10/96). LA (submitted on 11/18/97). EPA on 10/14/97). 06." Annual Book of ASTM Standards. "Standard Practice for Vacuum Distillation of Solvents from Solvent-Reducible Paints for Analysis. 13. (8) EPA Reference Method 311. D. Solid Phase Microextraction." Artrtual Book of ASTM Standards. Censullo.J. A complete list of J.05. Petition also submitted by Albermarle Corp. Washington.B.Golden Gate Society Technical Committee used for d e t e r m i n a t i o n of h a z a r d o u s air p o l l u t a n t s (HAPs).K. Vol.01. Thanks are extended to the following i n d i v i d u a l s for their partici p a t i o n in the r o u n d robin study: Robert Shirey. J." Final Report to the California Air Re sources Board. 69.S." En vironmentd Science and Technology." Annual Book of Starzdards. D 2369. (13) (14) (15) (16) References (1) EPA Reference Method 24. Appendix A. Boyd Boland. Refer to CFR 40.T. A k z o Coat ings. 1997. a n d U. Philip Analytical Company. (3) Arco Chemical Company (submitted to U. American Society for Testing Materials.. "Practice for Determining the Precision Data of ASTM Methods for Analysis and Testing of Industrial Chemicals. Ding a n d Santos P. Chai. (11) (12) ACKNOWLEDGMENTS The authors wish to thank Darick X. for their participation in this project. American Society for T e s ~ g and Materials. West Conshohocken. A n internal s t a n d a r d can easily be incorporated prior to dis t i l l a t i o n .ASTM Meeting. 06. "Test Method for Volatile C o n tent of Coatings.Alameda. in preparation. VoL 06.S. Baton Rouge.." Annual Book of ASTM Start dards. Wiley VCH. "Improvement of Speciation Pro files for Aerosol Coatings. 28. American Society for Testing and Materials. Y. We also t h a n k Pacific Coast Lacquer.. No.T.. M. West C onshohocken. EPA on 1/17/97). affiliated withffie Synthetic Organic Chemical Manufacturers Association.S.. American Society for Testing and Materials. Vol. "'New Solvent Free Sample Preparation Tectmiques Based on Fiber and Polymer Technologies. D 3272. West Conshohocken.52. Wills.C." Avail able fromSuperintendent of Documents. Sarabia.. A. A t h e y Technologies.Z. Density..C. (2) D ~janusz/spme pub. West Conshohocken.S. and Weight Solids of Surface Coatings. (9) Results presented by Sub-Committee DO1.1995. M. Inc. Zhang. and Gorecki.01. Ford Motor C o m p a n y .01.uwaterloo. Volume Solids. Government Printing Office. Part 63. Yang. M. Dr. "Improvement of Speciation Profiles for Architectural and Industrial Maintenance Coating Operations. (4) Dibasic Esters Group. Appendix A. Pawliszyn's SPME papers is available on the world wide web at http://sciborg. "Determina tion of Volatile Matter Content." Final Report to the California Air Resources Board.S.S. Luo. D." Annual Book of ASTM Standards. PA. No. 33 (1997). June 26.C. and Jones. (5) Enviro Tech International. GA. Inc. June 1996.21. s t u d e n t s at California Polytechnic State University." Available from Su perintendent of Documents.. Refer to CFR 40.. PA. Part 60. San Luis Obispo. CA (submitted to U. (submitted to U. Lorraine DaSilva. Vol. "Analysis of Hazardous Air Pollutant Compounds in Paints and Coatings by Direct Injection Into a Gas Chromatograph. (7) D 3271. Atlanta. West Conshohocken. "'Direct VOC Analysis of Water Based Coatings by Gas Chromatography and Solid Phase Microextraction. (10) Censullo." JOURNAL COATINGS OF TECHNOLOGY.. U. T . PA. J. a n d the d i s t i l l a t e m a y be c h r o m a t o g r a p h e d on a n y suitable capri lary c o l u m n w i t h o u t d i s r u p t i n g the in tegrity of the chromatographic system b e i n g used. "Standard Practice for Direct Injectionof Solvent Reducible Paints into a Gas Chromatograph for Solvent Analysis. Pawliszyn. (6) Los Angeles Society for Coatings Technology. "'Practice for Determining Vola tile Organic Compound (VOC) Content of Paints and Related Coatings. D.. (16) 74 Journal Coatings Technology of . Wash ington. Vol. 06.htmL E 180-94. A. D. Government Printing Office. PA. 15. Wills. Inc.C. A. M . Robert Athey. 869.