Even though the correlation factor can be used without prior the use Of this Of the parent correlation factor for a CIB separation with an aluminum oxide aromatic ring class preparation step should provide a powerful analytical tool for overall characterization of hydroaromatics and aromatic hydrocarbons in complex samples.
LITERATURE CITED (1) H. W. Sternberg, R. Raymond, and F. K. Schweighardt, Science, 188,
49 (1975). (2) H. W. Sternberg, R. Raymond, and F. K. Schweighardt, Prepr., Div. Pet. Chem., A m . Chem. Soc., 21 (l),198 (1976). (3) S.A. Holmes, P. W. Woodward, G. P. Sturm, J. W. Vogh, and J. E. Dooley, ERDA BERC RI-76/10,1976. (4) M. Farcasiu, Fuel, 56,9 (1977). (5) J. E. Schiller, Prepr., Div. Pet. Chem., Am. Chem. Soc., 22 (2),638
(, 1 . -9 7 7.,.\ (6) D. L. Wooton, W. M. Coleman, H. C. Dorn, and L. T. Taylor, Prepr., Div. Pet. Chem., A m . Chem. Soc., 22 (2),634 (1977). (7) H. C. Dorn and D. L. Wooton. Anal Chem.. 48. 2146 (1976). (8j S. E. Scheppele, G. J. Greenwood, P. L. Grizzle, T. D. Marriott, C. S. HSU, N. E. Perreira, P. A. Benson, K. N. Detwiler, and G. M. Stewart, Prepr., Dlv. Pet. Chem., A m . Chem. Soc., 22 (2),665 (1977). (9) S.E. Scheppele, P. L. Grizzle, G. J. Greenwood, T. D. Marriott, and N. E. Perreira, Anal. Chem., 46,2105 (1976). (10) J. W. Prather, A. R. Tarrer, J. A. Guin, D. R. Johnson, and W . C. Neeiy. Prepr., Div. Fuel Chem., Am. Chem. Soc., 21 (5), 144 (1976).
(11) L. R. Snyder, "Principles of Adsorption Chromatography", Marcel Dekker, New York, N.Y., 1968. (12) R. J. Hurtubise, J. F. Schabron, J. D. Feaster, D. H. Therkildsen, and R. E. Pouison, Anal Chim. Acta, 89, 377 (1977). (13) E. J. Kitka, Jr., and E. Grushka, Anal. Chem., 48, 1098 (1976). (14) R. E. Sleight, J . Chromatogr., 83, 31 (1973). (15) Mobil R&D Corp., EPRI Project RP 410-1 (1976). (16) L. E. Furlong, E. Effron, L. W. Vernon, and E. L . Wilson, Chem. Eng. Progr., August, pp 69-75 (1976). (17) Hydrocarbon Research, Inc., EPRI Project FR 389 (1976). (18) G. Doyle, Prepr., Div. Pet. Chem., Am. Chem. Soc., 21 (l),165 (1976). (19) R. C. Neavel, Fuel, 55, 237 (1976). (20) W. Bertsch, E. Anderson, and G. Holzer, J. Chromatogr., 126, 213 (1976). (21) R. A. Friedel and M. Orchin, "Ultraviolet Spectra of Aromatic Compounds", John Wiiey & Sons, New York, N.Y., 1951. (22) E. L. Eiiei, "Stereochemistry of Carbon Compounds", McGraw-Hill Book Company, New York, N.Y., 1962,p 195. (23) D. C. Locke, J . Chromatogr. Sci., 12, 433 (1974). (24) V. Martinu and J. Janik, J . Chromatogr., 65,477 (1972). RECEn-ED for review June
21.1977. AcceDted August 30.1977. presented in part at the 174th National ~ ~ i& the t i American Chemical Society, Chicago, Ill., August 1977. Financial support was provided by United States Energy Research and D.C.$ Contract No. E (49 -18)-2367.
Open-Pore Polyurethane Columns for Collection and Preconcentration of Polynuclear Aromatic Hydrocarbons from Water James D. Navratil Rockwell International, Rocky Flats Plant, Golden, Colorado 8040 7
Robert E. Sievers" and Harold F. Walton Department of Chemistry, University of Colorado, Boulder, Colorado 80309
Open-pore polyurethane (OPP) columns are prepared by issiiu polymerization of toluene-carbon tetrachloride solutions of an isocyanate and a polyol. Columns of OPP have been tested for Ion-exchange properties, solvent compatibilities, and ability to remove and concentrate polynuclear aromatic hydrocarbons (PAH) from water. Solutions containing 1 yg of pyrene per liter of water have been concentrated 200-fold by passing 1000 mL through a 0.3 X 5 cm column and eluting the pyrene with 5 mL of methanol. Recovery of pyrene was approximately 100 YO. Results of comparisons of breakthrough capacities and elution rates for PAH on OPP, Amberlite XAD-2, and Bio-Rad AG MP-50 are presented.
This paper deals with the comparison of in-situ formed open-pore polyurethane (OPP) with other new materials for the removal and concentration of polynuclear aromatic hydrocarbons (PAH) from water. O P P has also been tested for ion-exchange properties, solvent compatibilities, and other characteristics. OPP is composed of agglomerated spherical particles (1to 10 Fm in diameter) bonded to each other in a rigid, highly permeable structure (1-4). We have shown scanning electron micrographs of O P P in a recent publication ( 4 ) . It was first used in a column by Ross and Jefferson in 1970 (1). OPP was 2260
ANALYTICAL CHEMISTRY, VOL. 49, NO. 14, DECEMBER 1977
also used as an efficient gas chromatographic support (2) and for liquid chromatography separations with nonaqueous solvents (3, 4). No study has been reported, t o the best of our knowledge, in which O P P has been used for removing organic compounds from water. Much work has been reported, however, on the use of cellular (foamed) polyurethane for the collection, separation, and recovery of various inorganic and organic components from aqueous solution ( 5 ) . Polyurethane foam plugs were investigated as a replacement for carbon as a sorbent for preconcentration of organics prior to analysis (6) and for removal of organics from wastewater (7). Foam plugs were used successfully for the preconcentration of polychlorinated biphenyls (8-10) and chlorinated insecticides ( I O ) from water. For oil concentration from water, polyurethane gave a lower collection efficiency than liquid-liquid extraction ( I I ) , and for several organic compounds including naphthalene, polyurethane foams were not as effective as chloroform extraction and Amberlite XAD resin sorption (12). Other than naphthalene, sorbtion of PAH on polyurethanes has not been tested. Table I shows the structures of the PAH studied. Carbon adsorption, liquid-liquid extraction, reverse osmosis, and macroreticular resins have been studied for the preconcentration of PAH from water (7,13). The most popular methods have been the use of Amberlite XAD macroreticular resins
Table 111. Compatibility of OPP with Various Solvents Maximum pump Weight loss, % b Solvent pressure, lb/in.’ a Acetone 3 3 0 t 10 ... Heptane >330 -1.2 Ethanol >330 -1.2 Methanol >330 -1.2 1 M HC1 175 k 5 -7.6 1 M HNO, 3 3 0 i 10 + 1.2 1 M H,SO, 113 i 47 ...
T a b l e I . Polycyclic Aromatic Hydrocarbons Studied.
Compound
Structure
Benzo Cal pyrene (Aldrich, 9 8 % ) Blphenyl
H, 0 0.1 M NH, 1 M NH, 1 M NaOH
Fluoranthene (Aldrich, 9 8 % ) Nophthalene (Baker, reagent) 6-
Pyrene ( K B K , reopento)
d
4-
-=
Tablea. Materials and Reaction for Preparation of Open-Pore Polyurethane of Various Compositions. Grams of Material per 25 ml Solvent Trade Name
Structure
Mondur M R
OCN~C~QNCO
LA-475 (Union Carbide Carp.)
OH/NCO=I.O OH/NCOm2.2
-
3.16
2.00
2.84
4.00
CH2*NCO
OH cHgcH-c%r
O
H
1
N- I C H ~ - C H L - N ( C H L ~ ~ ~ C H ~ ~ ~ L
Reaction:
RNCO
+
R’OH
-3.5 -1.1
k
‘ P J r i f 8 t d f u r t h e r by wblimation
(Mobay Chemical Co.)
-2.5
...
a Pressure to break the OPP to glass column bond after storage of OPP columns ( 5 cm long) in solvent for 1 week. After passage of 1 L of solvent through OPP column 1 0 cm long.
A
Phenanthrene (Motheson, technical‘)
250 * 1 2 15. 5 85 i 1 5
