Extraction and determination of polycyclic aromatic
hydrocarbons from domestic stove aerosol
Citation for published version (APA):
Claessens, H. A., Lammerts van Bueren, L. G. D., & Ven, van de, P. M. (1986). Extraction and determination of polycyclic aromatic hydrocarbons from domestic stove aerosol. Journal of Aerosol Science, 17(3), 639-642. https://doi.org/10.1016/0021-8502(86)90178-3
DOI:
10.1016/0021-8502(86)90178-3
Document status and date: Published: 01/01/1986
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J. Aerosol Sci.. Vol. 17, No. 3, pp. 639-642, 1986. 0021-8502/86 $3.00+0.00 Printed in Great Britain. Pergamon Journals Ltd.
E X T R A C T I O N A N D D E T E R M I N A T I O N O F P O L Y C Y C L I C A R O M A T I C H Y D R O C A R B O N S F R O M D O M E S T I C S T O V E
A E R O S O L
H. A.
CLAESSENS,
L. G. D. LAMMERTS VAN BUEREN* and P. M. VAN DE VENEindhoven University of Technology, Department of Chemical Engineering, Laboratory of Instrumental Analysis, P.O. Box 513, 5600 MB Eindhoven, The Netherlands
I N T R O D U C T I O N
Polycyclic aromatic compounds (PAC) is a collective noun of compounds, of which many have mutagenic and carcinogenic properties (Bjorseth, 1983; Lee et al., 1981). Like the parent polycyclic aromatic hydrocarbons (PAH), PAC may be divided into a number of subclasses; amino, nitro, cyano polycyclic aromatic hydrocarbons, etc.
To study the effects o f stove emission of PAC and other components on the environment and health, and to support new stove design, reliable analytical procedures must be available. Because of the high toxic properties of PAH, the development of extraction and analytical procedures in domestic stove smoke aerosol was o f first interest.
For these samples the analytical procedure generally includes an extraction and a clean-up or pre-fractionation step, followed by the proper analytical stage.
In this paper we concentrate on the problems encountered in the development of extraction techniques for PAH from aerosol samples of stove smoke.
The organic part of the collected aerosol samples, which contain PAH, is generally separated from the inorganic part by solvent extraction procedures. PAH are soluble in many organic solvents like acetone, methanol, dichloromethane, cyclohexane, toluene, dimethyl- sulfoxide, etc. Many o f these solvents or mixtures are advocated for the extraction of the organic part o f the aerosol (Pitts et al., 1978; B a r t o n et al., 1979).
The extractions are generally carried out by a Soxhlet procedure or as an attractive alternative by ultrasonic agitation. The efficiency of the various available procedures depends on the chemical and physical structure of the sample, properties of the extraction solvent and extraction conditions such as time and temperature. The physical and chemical nature o f the collected aerosol sample play an important role in extraction efficiencies (Fitc and Smith, 1979; Griest et al., 1980). Domestic stove smoke aerosol partly consists of carbonaceous particles of small size ranges ( < 10 ~m), so exposing a large adsorption area. This may strongly adsorb PAH and other components and decrease extraction efficiency considerably, as will be shown later.
An attractive alternative for the Soxhlet extraction method is the ultrasonic agitation technique as the latter is less time-consuming and offers the opportunity to extract samples at ambient or other temperatures. In our investigations we favoured low-boiling, non-UV- adsorbing extracting liquids. This allows the extracting agent to be evaporated easily in order to raise PAH concentrations to facilitate the detectability. Moreover, UV-adsorbing liquids interfere with the proper UV-detection of PAH components in the sample.
In this work a number of extraction liquids were tested, applying both the Soxhlet method and ultrasonic agitation as extraction techniques. The extraction procedures were applied to blank, real and spiked aerosol samples and the results were compared.
The analytical procedure to determine PAH after extraction of the aerosol exhaust is based on high-performance liquid chromatography (HPLC) for both the clean-up and analysis step.
* Present address: DSM Research, Analytical Department, P.O. Box 18, 8160 M D Geleen, The Netherlands. 639
640 H . A . CLAESSENS, L. G. D. LAMMERTS VAN BUEREN and P. M. VAN DE VEN
Fluorescence and UV techniques are used for the detection of the separated PAH. The analytical procedure is applied routinely in our laboratory. A detailed discussion of these methods is beyond the scope of this paper. Figure 1 shows a c h r o m a t o g r a m of the separation of a standard solution of the 16 P A H under investigation by H P L C .
E X P E R I M E N T A L M E T H O D
All chemicals and solvents were of analytical grade (Merck, Darmstadt, F.R.G.) except petroleumether (Shell Rotterdam, The Netherlands). Standards of the 16 Priority Pollutant P A H were from Serco Inc. Roseville Minn., U.S.A., and include: 1 = naphtalene, 2 = acenaphtalene, 3 = acenaphtene, 4 = f l u o r e n e , 5 = phenanthrene, 6 = anthracene, 7 = fluoranthene, 8 = pyrene, 9 = benzo(a)anthracene, 10 = chrysens, 11 = benzo(b)-
fluoranthene, 12 = benzo(k)fluoranthene, 13 = benzo(a)pyrene, 14 = benzo(g,h,i)-
perylene, 15 = dibenzo(a,h)anthracene and 16 = indeno(1,2,3-c,d)pyrene.
Extractions were carried out in standard laboratory glassware. The H P L C equipment for the pre-fractionation and analytical steps was constructed of several manufactured parts.
Domestic stove smoke aerosol from hard wood as fuel was sampled by the filter collection technique on glass fiber filters, of which a representative part was subjected to the extraction procedure. Samples were stored in the dark in closed vessels at a temperature of - 16°C and extracted and analyzed within a few days.
Three low-boiling extraction liquids: diethylether, dichloromethane and petroleumether, were tested. The relatively high-boiling dimethylsulfoxide (DMSO) was also applied as an extractant.
Both the Soxhlet extraction technique and ultrasonic agitation were investigated. Typical extraction time for the Soxhlet procedure was 16h; the extraction was carried out under nitrogen and protected from light to avoid P A H losses from the sample. Under the ultrasonic agitation technique the sample was sequentially treated four times for 10 min with the extractant and afterwards the extracts were collected. F o r both techniques the extract was then evaporated under a gentle N2-stream prior to the pre-fractionation.
I0 12 13 6 II 8 Injection 14 15 I I I I I 0 I 5 I0 15 I Time (rain) 16 U V signol 16 Fluorescence signal I 2O
Fig. 1. lsocratic separation of a standard solution o f the 16 P A H under investigation. Elutent: water-acetonitrile, 22:78 v/v; Column: 2 0 0 x 3 . 0 m m with Vydac 201 T P as stationary phase;
Polycyclic aromatic hydrocarbons from domestic stove aerosol 641 Five e x t r a c t i o n p r o c e d u r e s were tested:
I. U l t r a s o n i c a g i t a t i o n with d i e t h y l e t h e r at a m b i e n t t e m p e r a t u r e , 11. U l t r a s o n i c a g i t a t i o n with d i c h l o r o m e t h a n e at a m b i e n t t e m p e r a t u r e , III. S o x h l e t e x t r a c t i o n with p e t r o l e u m e t h e r ,
IV. S o x h l e t e x t r a c t i o n with d i c h l o r o m e t h a n e ,
V. t I l t r a s o n i c e x t r a c t i o n with d i m e t h y l s u l f o x i d e at 100°C.
F r o m the c h r o m a t o g r a p h i c d a t a such as r e t e n t i o n times, peak height a n d area, q u a l i t a t i v e and q u a n t i t a t i v e i n f o r m a t i o n o f P A H in the sample c o u l d be o b t a i n e d .
R E S U L T S
T o test the r e c o v e r i e s o f the five selected e x t r a c t i o n p r o c e d u r e s , b l a n k filters spiked with k n o w n q u a n t i t i e s o f the 16 P A H were e x t r a c t e d a n d analyzed. F o r the five e x t r a c t i o n m e t h o d s r e p r o d u c i b l e recoveries o f at least 95 ?o for the 16 P A H were estimated. F o r the w h o l e p r o c e d u r e o f e x t r a c t i o n a n d analysis, r e p r o d u c i b l e results o f 90 ~o were d e t e r m i n e d for all P A H c o m p o n e n t s .
A n u m b e r o f identical a e r o s o l samples were then extracted a c c o r d i n g to p r o c e d u r e s I - V and analyzed.
T o c o m p a r e the different e x t r a c t i o n p r o c e d u r e s the r e c o v e r y d a t a were calculated t a k i n g the results o f m e t h o d 1 as unity. T h e s e results are s u m m a r i z e d in T a b l e 1.
F o r these types o f samples, it is q u e s t i o n a b l e w h a t p e r c e n t a g e o f the a d s o r b e d a n d e n c a p s u l a t e d P A H m a t e r i a l is extracted by a certain e x t r a c t i o n p r o c e d u r e . T h e r e f o r e , a n u m b e r o f a e r o s o l samples were spiked with k n o w n a m o u n t s o f P A H a n d i m m e d i a t e l y a f t e r w a r d s extracted and analyzed. F o r m e t h o d s I, II a n d V the results are s u m m a r i z e d in T a b l e 2.
Table 1. PAH recoveries of aerosol samples from five selected extraction procedures; results refer to extraction method I. - = Not detected with ether extraction in that typical sample; 0.0 = not detectable with
the corresponding extractant
Extraction method Component 1 II 111 IV V Phenantrene 1.0 0.5 - 0.1 - -Fluoranthene 1.0 0.8 1.5 0.3 - - Benzo(a)anthracene 1.0 1.5 1.2 1.6 - - Benzo(bjfluoranthene 1.0 1.3 0.5 1.6 1.2 Benzo(k)fluoranthene 1.0 1.5 2.2 1.3 0.8 Benzola)pyrene 1.0 1.4 0.0 1.6 1.5 Bcnzolg,h,i)perylene 1.0 - 0.0 - - 1.0 lndeno(1,2, 3-cd)pyrene 1.0 - - 0.0 - - 1.1 Table 2. Recoveries of PA H spiked aerosol samples in percentages of added
PAH amounts Extraction method Component I ~ ) 1 H v Naphtalene Acenaphtalene Phenantrene Anthracene Fluoranthenc Pyrene Benzo(a)anthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Dibenzo (a,h)anthracene Benzo(g,h,i)perylene Indeno(1,2,3-cd)pyrene 0 0 0 0 0 0 137 64 22 87 25 37 66 65 77 46 64 81 60 71 98 56 68 110 60 69 82 66 75 93 63 73 91 54 66 87 32 57 92 40 75 107 AS !'if: J-Y
642 H.A. CLAESSENS, L. G. D. LAMMERTS VAN BUEREN and P. M. VAN DE VEN
F r o m these results it can be c o n c l u d e d that the recoveries o f the spiked material are poor.
D I S C U S S I O N A N D C O N C L U S I O N S
F r o m the experiments and results on P A H spiked blank filters it appears that reliable extraction and analysis procedures are available for simple n o n - a d s o r b i n g sample matrices. F o r the aerosol samples under investigation the relative efficiencies for the different P A H and extraction m e t h o d s are questionable.
The results o f Table 1, in which a large n u m b e r o f identical aerosol samples are treated, show different recoveries for the several P A H c o m p o n e n t s . This might be due to the different molecular structures o f P A H , as there are linear a n d angular annulated ring systems. Efficiency variations f r o m o n e - t o - o n e correlation to 6 0 ~ , deviation between the several extraction procedures are observed. F r o m these data it is hard to decide which percentage o f P A H material is extracted.
Besides w o r k i n g with labeled P A H a n o t h e r a p p r o a c h to gain further insight in this subject is the spiking o f k n o w n a m o u n t s o f P A H on aerosol samples, a n d the determination o f P A H after equilibrium. T h e results for the extraction m e t h o d s I, II and V are summarized in Table 2, indicating p o o r efficiencies for the m e t h o d s I and II, while m e t h o d V tends to p r o d u c e better results, especially for the 4 and higher a r o m a t i c ring systems. But with this a p p r o a c h it is uncertain whether the spiked P A H material behaves the same as the original P A H aerosol deposited during sampling.
F r o m these results it can be concluded that extraction efficiencies m a y differ strongly for several extraction procedures within one type o f sample.
This study has shown that extraction procedures o f P A H and related c o m p o u n d s should be selected and evaluated carefully d e p e n d i n g on the type o f sample under investigation.
F u r t h e r investigation on this subject in o u r l a b o r a t o r y will include a.o. a study o f what processes control the strong a d s o r p t i o n o f P A H and related c o m p o n e n t s by taking an insight into the physical and chemical nature o f the aerosol sample, so allowing the development o f p r o p e r extraction strategies for these types o f samples.
R E F E R E N C E S
Barton, S. C., Johnson, N. D. and Das, B. S. (1979) Final Report to Air Resourches Branch Canadian Ministry of Environment: A feasibility study of alternatives to high-volume sampling for labile constituents of atmospheric particulates. Ontario Research Foundation, Ontario, Canada.
Bjorseth, A. (Ed.) (1983) Handbook of Polycyclic Aromatic Hydrocarbons. Marcel Dekker, New York.
Fitc, W. L. and Smith, D. H. (1979) Environ. Sci. Technol. 13, 341.
Griest, W. H., Yeatts, L. B. Jr. and Caton, J. E. (1980) Analyt. Chem. 52, 199.
Lee, M. L., Novotny, M. V. and Bartle, K. D. t1981) Analytical Chemistry of Polycyclic Aromatic Hydrocarbons.
Academic Press, New York.
Pitts, J. N. Jr., Van Cauwenberghe, K. A., Grosjean, D., Schmid, J. P., Fitz., D. R., Belser, W. L., Knudson, G. B. and
Hynds, P. M. (1978) Science 202, 515.
