Organic Marine Geochemistry - American Chemical Society

12 Polychlorinated Biphenyls and Hydrocarbons Distributions among Bound and Unbound Lipid Fractions of Estuarine Sediments 1

H . R. Beller and B. R. T. Simoneit

Downloaded by AUBURN UNIV on January 10, 2018 | http://pubs.acs.org Publication Date: April 21, 1986 | doi: 10.1021/bk-1986-0305.ch012

Environmental Geochemistry Group, College of Oceanography, Oregon State University, Corvallis,OR97331

Selective extraction was used to operationally determine the quantitative and qualitative distributions of PCB's and saturated hydrocarbons among free l i p i d (FL), humic acid (HA), and humin (HU) fractions of four contaminated estuarine sediments. In all samples, over 90% of the total sedimentary PCB's and hydrocarbons were extracted with FL fractions. Bound (HA and HU) and free assemblages of these compounds may have derived from different sources. Two polar, chlorinated pollutants also detected i n this study, hexachlorophene (HCP) and pentachlorophenol (PCP), were proportionately more concentrated i n bound fractions than the non-polar compounds; HCP was detected only i n HA fractions and was probably chemically bound to refractory organic matter. Selective extraction is a promising technique for investigating strongly bound polar pollutants, such as HCP, which apparently are not recovered by conventional solvent extraction. Suspended and bottom sediments are widely regarded as a sink for PCB's and other hydrophobic organic pollutants released into aquatic systems. The mechanism commonly proposed to explain the affinity of PCB s for sediments i s equilibrium sorption or partitioning, which is a function of the aqueous solubility of PCB isomers and the attractiveness of the sedimentary matrix to PCB s (1-4) . Field and laboratory studies indicate that sedimentary organic matter plays a fundamental role i n PCB-sediment associations (5-12) and that humic substances are important components of the sedimentary organic mat r i x for such associations (6,13-16). For example, Choi and Chen (6) found that sedimentary PCB and DDT concentrations were linearly related to the humic acid content of sediments from Los Angeles Harbor. Pierce et a l . (15) determined that humic acid could account 1

1

Current address: Tetra Tech, Inc., 11820 Northup Way, Bellevue, WA 98005.

1

0097-6156/ 86/ 0305-0198506.00/ 0 © 1986 American Chemical Society

Sohn; Organic Marine Geochemistry ACS Symposium Series; American Chemical Society: Washington, DC, 1986.


12.

BELLER AND SIMONEIT

PCBs and Hydrocarbons

199

f o r over h a l f the s o r p t i o n c a p a c i t y o f marine sediments i n a l a b o r a t o r y experiment i n v o l v i n g ρ,ρ'-DDT; s i m i l a r r e s u l t s were o b t a i n e d i n an experiment w i t h h e x a c h l o r o b u t a d i e n e ( 1 3 ) . More r e c e n t s t u d i e s have demonstrated t h a t PCB isomers and DDT can become a s s o c i a t e d w i t h o r i n c o r p o r a t e d i n t o d i s s o l v e d humic substances (17-19) and L i c h t e n s t e i n e t a l . have shown t h a t ρ,ρ'-DDT can become p a r t i a l l y "bound" ( s o l v e n t i n e x t r a c t a b l e ) i n wetted s o i l s a f t e r b r i e f i n c u b a t i o n ( 2 0 ) . W h i l e the i n c o r p o r a t i o n o f s y n t h e t i c , h y d r o p h o b i c p o l l u t a n t s i n t o r e f r a c t o r y o r g a n i c m a t t e r has been i m p l i c a t e d by t h e s e s t u d i e s , i t has not been e x p l i c i t l y i n v e s t i g a t e d i n the f i e l d . The o b j e c t i v e of t h i s s t u d y was t o d e t e r m i n e , by s e l e c t i v e e x t r a c t i o n , whether o r not n o n - p o l a r , n o n - i o n i c p o l l u t a n t s ( e . g . , PCB's and p e t r o l e u m h y d r o c a r b o n s ) can become "bound" i n n a t u r a l s e d i m e n t s , and, i f s o , whether t h e i r q u a l i t a t i v e d i s t r i b u t i o n s p r o v i d e i n f o r m a t i o n about the i n c o r p o r a t i o n p r o c e s s . The i n c o r p o r a t i o n o f n o n - p o l a r compounds i n t o s e d i m e n t a r y o r g a n i c m a t t e r i s o f i n t e r e s t i n a pure g e o c h e m i c a l s e n s e , but a l s o has p r a c t i c a l e n v i r o n m e n t a l i m p l i c a t i o n s . "Bound" p o l l u t a n t s would be u n d e t e c t e d i n many e n v i r o n m e n t a l s t u d i e s because such s t u d i e s t y p i c a l l y employ s i m p l e s o l v e n t e x t r a c t i o n ; the q u a n t i t a t i v e s i g n i f i c a n c e o f bound p o l l u t a n t s must be a s c e r t a i n e d t o produce an a c c u r a t e assessment o f c o n t a m i n a t i o n . A l s o , the b i o l o g i c a l a v a i l a b i l i t y of s e d i m e n t a r y p o l l u t a n t s c o u l d depend on the n a t u r e o f t h e i r a s s o c i a t i o n w i t h o r g a n i c m a t t e r . For example, "bound" PCB's entrapped w i t h i n humic m a t r i c e s might be l e s s a c c e s s i b l e t o b e n t h i c fauna than " f r e e " PCB's. Methods F i g u r e 1 p r e s e n t s a f l o w diagram o f the s e l e c t i v e e x t r a c t i o n p r o c e d u r e . T h i s procedure was d e s i g n e d t o e f f e c t e x h a u s t i v e e x t r a c t i o n s at each s t a g e and t o t r e a t F L , HA, HU f r a c t i o n s as s i m i l a r l y as p o s s i b l e . D r i e d sediment samples ( c a . 90 t o 140 g, d r y wt) were S o x h l e t e x t r a c t e d w i t h a z e o t r o p i c t o l u e n e / m e t h a n o l ( 1 : 3 , v/v) f o r over 95 hr ( c a . 115 c y c l e s ) w i t h a s o l v e n t change a t 30 h r ; a l l s o l v e n t s used were d i s t i l l e d - i n - g l a s s and o f h i g h p u r i t y ( B u r d i c k and Jackson)· Humic s u b s t a n c e s were e x t r a c t e d w i t h f i v e s u c c e s s i v e one l i t e r a d d i t i o n s o f s o l v e n t - c l e a n e d 0.2 Ν Κ0Η. The combined aqueous e x t r a c t was f i l t e r e d t h r o u g h a Whatman GF/A g l a s s f i b e r f i l t e r ( t o remove suspended sediments from the e x t r a c t ) , a c i d i f i e d ( t o p r e c i p i t a t e the humic a c i d ) , and r e - f i l t e r e d ( t o s e p a r a t e humic and f u l v i c a c i d s ) . The humic a c i d p r e c i p i t a t e was r i n s e d t h r o u g h the f i l t e r w i t h 0.2N KOH, r e s u l t i n g i n a b a s i c humic e x t r a c t w i t h o u t f i n e p a r t i c l e s . The f i l t e r s and t r a p p e d p a r t i c l e s were added t o the r e s i d u a l sediment. The purpose of s a p o n i f y i n g humic f r a c t i o n s was to d i s p e r s e the polymers i n the presence o f o r g a n i c s o l v e n t s , thus r e l e a s i n g entrapped o r sorbed compounds. The FL e x t r a c t s were s a p o n i f i e d t o make them comparable t o HA and HU f r a c t i o n s . The s t r o n g base used t o s a p o n i f y FL, HA, and HU f r a c t i o n s c o n v e r t e d DDT ( d i c h l o r o d i p h e n y l t r i c h l o r o e t h a n e ) t o DDE ( d i c h l o r o d i p h e n y l d i c h l o r o e t h y l e n e ) by d e h y d r o h a l o g e n a t i o n ; t h u s , DDT i s r e p o r t e d as DDE i n t h i s s t u d y . S e p a r a t o r y f u n n e l e x t r a c t i o n s of s a p o n i f i e d e x t r a c t s were c a r r i e d out a t >pH 12 and

m r r m

CO

O R G A N I C M A R I N E GEOCHEMISTRY

2 1 0

Free Lipid


STD

1

2 ' β Μ ' 5 ' 6' 7 PCP

1

8

1

9 ΊΟ

HCP

Humic Acid

Il

STD

J L 1

2 « e U 5 '6' 7 PCP 1

8

1

910

Humin STD

τ

2 3 4 ' 5 T' c6T ' 7 Π Γ

Τ

8

9 ΊΟ

F i g u r e 5. C a p i l l a r y GC-ECD t r a c e s o f F L , HA, and HU f r a c t i o n s o f sample HR. PCP - p e n t a c h l o r o p h e n o l ( a s m e t h y l e t h e r d e r i v a t i v e ) ; HCP - hexachlorophene ( a s d i m e t h y l e t h e r d e r i v a t i v e ) ; STD - deca c h l o r o b i p h e n y l . Approximate PCB homolog e l u t i o n ranges a r e delineated.



12.

BELLER A N D SIMONEIT

211


sample d i f f e r e n c e s i n p h e n o l i c d i s t r i b u t i o n s were c o n t r o l l e d by f a c t o r s o t h e r t h a n the pH o f S o x h l e t e x t r a c t i o n ( w h i c h was the same f o r a l l samples). The d e t e c t i o n of HCP i n e n v i r o n m e n t a l samples i s noteworthy not o n l y because o f i t s unique d i s t r i b u t i o n , but a l s o because i t i s seldom r e p o r t e d i n e n v i r o n m e n t a l l i t e r a t u r e . A p p a r e n t l y , o n l y two papers document e n v i r o n m e n t a l HCP d i s t r i b u t i o n s and b o t h were w r i t t e n i n the e a r l y t o mid 1970's. HCP c o n c e n t r a t i o n s i n the ppb range were r e p o r t e d f o r m u n i c i p a l sewage e f f l u e n t s (52) and f o r water and sediments near sewage o u t f a l l s (55) . The commercial use of HCP, a p o w e r f u l b a c t e r i o s t a t i c agent and g e r m i c i d e , has been g r e a t l y r e duced s i n c e a ban was i n s t i t u t e d by the FDA i n 1972. However, HCP i s v e r y p e r s i s t e n t : a l a b o r a t o r y s t u d y r e v e a l e d t h a t HCP was appar e n t l y not degraded i n r i v e r water and had a " h a l f l i f e " o f 290 days i n e s t u a r i n e sediments a t 22 °C ( 5 6 ) . F u r t h e r m o r e , the environmen t a l r e l e a s e of HCP a f t e r 1972 i s p l a u s i b l e s i n c e some h o s p i t a l s s t i l l use the c h e m i c a l and may d i s c h a r g e t h e i r e f f l u e n t s t h r o u g h m u n i c i p a l sewage treatment p l a n t s . PCP, a g e n e r a l b i o c i d e w i d e l y used as a wood p r e s e r v a t i v e , may a l s o have been c h e m i c a l l y bound t o s e d i m e n t s , a l t h o u g h the e v i d e n c e f o r t h i s i s not as s t r o n g as t h a t f o r HCP. T a b l e V, w h i c h p r e s e n t s PCP c o n c e n t r a t i o n s f o r FL, HA, and HU f r a c t i o n s o f a l l samples, shows t h a t PCP was a more s i g n i f i c a n t component o f bound f r a c t i o n s than were the l e s s p o l a r PCB's. S i m i l a r l y , Murthy e t a l . found t h a t PCP and a m i c r o b i a l l y m e t h y l a t e d m e t a b o l i t e , p e n t a c h l o r o a n i s o l e , bound t o HA and HU f r a c t i o n s of a e r o b i c and a n a e r o b i c s o i l s over a 24 day l a b o r a t o r y i n c u b a t i o n p e r i o d (57)· T a b l e V.

R e l a t i v e PCP

Sample NB(0-3) NB(29-31) HR LA

D i s t r i b u t i o n s (as % of t o t a l sed. cone.) FL 38% 74% 86% 94%

HA 17% 3% 9% 2%

HU 45% 23% 5% 3%

Conclusions 1) Over 90% of t o t a l s e d i m e n t a r y PCB's and p e t r o l e u m hydrocarbons were r e c o v e r e d w i t h FL f r a c t i o n s . 2) Q u a l i t a t i v e PCB and h y d r o c a r b o n d i s t r i b u t i o n s among o r g a n i c mat t e r f r a c t i o n s suggest t h a t f r e e and bound assemblages may d e r i v e from d i f f e r e n t s o u r c e s i n a g i v e n sediment. 3) P o l a r p o l l u t a n t s , such as c h l o r i n a t e d p h e n o l s , can occur l a r g e l y as c h e m i c a l l y bound components of r e f r a c t o r y o r g a n i c m a t t e r . 4) S e l e c t i v e e x t r a c t i o n c o u l d be a u s e f u l t e c h n i q u e f o r i n v e s t i g a t i n g c h e m i c a l l y bound p o l l u t a n t s , w h i c h are not d e t e c t a b l e by conventional solvent e x t r a c t i o n .


ORGANIC MARINE GEOCHEMISTRY

212 Acknowledgments

Samples and background information were generously provided by Bruce Brownawell and Dr. J. Farrington (New Bedford samples), Dr. R. Bopp (Hudson River sample), and Tony Phillips (Los Angeles sample). We thank Dr. F. I. Onuska for donating the 1:1:1 Aroclor standard and Dr. F. Prahl, James Butler, and Orest Kawka for their helpful com ments on the investigation and manuscript. Literature Cited 1.


2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24.

Bopp, R . F . ; Simpson, H . J . ; Olsen, C.R.; Kostyk, N. Env. S c i . & Tech. 1981, 15, 210-16. Chiou, C.T.; Peters, L.J.; Freed, V.H. Science 1979, 206, 83132. Dexter, R.N.; Pavlou, S.P. Mar. Chem. 1978, 7, 67-84. Pavlou, S.P.; Dexter, R.N. Env. S c i . & Tech. 1979, 13, 65-71. Abdullah, M . I . ; Kveseth, N.J.; Ringstad, O. Water, Air Soil Poll. 1982, 18, 485-97. Choi, W.W.; Chen, K.Y. Env. S c i . & Tech. 1976, 10, 782-86. Halcrow, W.; Mackay, O.W.; Bogan, J. Mar. Poll. B u l l . 1974, 5, 134-36. Hiraizumi, Y . ; Takahashi, M.; Nishimura, H. Env. S c i . & Tech. 1979, 13, 580-84. Karickhoff, S.W.; Brown, D.S.; Scott, T.A. Water Research 1979, 13, 241-48. Schwarzenbach, R.P.; Westall, J. Env. S c i . & Tech. 1981, 15, 1360-1367. Steen, W.C.; Paris, D.F.; Baughman, G.L. Water Research 1978, 12, 655-57. Wildish, D . J . ; Metcalfe, C.D.; Akagi, H.M.; McLeese, D.W. B. Env. Contam. Tox. 1980, 24, 20-26. Diachenko, G.W. Ph.D. Thesis, University of Maryland, 1981. Haque, R.; Schmedding, D. J. Env. S c i . Health 1976, B11, 129137. Pierce, R . H . , Jr.; Olney, C.E.; Felbeck, G.T., Jr. Geochim. Cosmochim. Acta 1974, 38, 1061-1073. Sawhney, B.L.; Frink, C.R.; Glowa, W. J. Env. Qual. 1981, 10, 444-48. Carter, C.W.; Suffet, I.H. Env. S c i . & Tech. 1982, 16, 735-40. Hassett, J.P.; Anderson, M.A. Env. S c i . & Tech. 1979, 13, 1526-1529. Landrum, P . F . ; Nihart, S.R.; Eadie, B.J.; Gardner, W.S. Env. Sci. & Tech. 1984, 18, 187-92. Lichtenstein, E . P . ; Katan, J.; Anderegg, B.N. J. Agric. Food Chem. 1977, 25, 43-47. Fales, H.M.; Jaouni, T.M.; Babashak, J.F. Anal. Chem. 1973, 45, 2302-2303. Ballschmiter, K . ; Zell, M. Fresenius Z. Anal. Chem. 1980, 302, 20-31. Duinker, J.C.; Hillebrand, M.T.J. Env. S c i . & Tech. 1983, 17, 449-56. Mullin, M.D.; Pochini, C.M.; McCrindle, S.; Romkes, M.; Safe, S.H.; Safe, L.M. Env. S c i . & Tech. 1984, 18, 468-76.


12.

BELLER AND SIMONEIT

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. 50. 51. 52. 53.


213

Onuska, F.I.; Kominar, R.J.; Terry, K.A. J. Chromatography 1983, 279, 111-18. Duinker, J.C.; Hillebrand, M.T.J.; Palmork, K.H.; Wilhelmsen, S. B. Env. Contam. Tox. 1980, 25, 956-64. Albro, P.W.; Corbett, J.T.; Schroeder, J.L. J. Chromatography 1981, 205, 103-11. Albro, P.W.; Parker, C.E. J. Chromatography 1979, 169, 161-66. Weliky, K . ; Suess, E . ; Ungerer, C.A.; Muller, P.J.; Fischer, K. Limnology and Oceanography 1983, 28, 1252-59. Summerhayes, C.P.; Ellis, J.P.; Stoffers, P.; Briggs, S.R.; Fitzgerald, M.G. WHOI Tech. Report, WHOI-76-115, 1977. Metcalf and Eddy, Inc. "Acushnet Estuary PCB's Data Management -Final Report"; for EPA Region I, 1983. Weaver, G. Env. S c i . & Tech. 1984, 18, 22A-27A. Weaver, G. "PCB Pollution in the New Bedford, Mass. Area: A Status Report", Mass. Coastal Zone Management, 1982. Bopp, R.F.; Simpson, H . J . ; Olsen, C.R.; Trier, R.M.; Kostyk, N. Env. S c i . & Tech. 1982, 16, 666-76. Hetling, L.; Horn, E . ; Tofflemire, J. "Summary of Hudson River PCB Study Results", N.Y. State D.E.C., Tech. Paper #51, 1978. Furukawa, K . ; Tonomura, K . ; Kamibayashi, A. Appl. Env. Microbiol. 1978, 35, 223-27. Bopp, R. J. Geophys. Research 1983, 88, 2521-2529. Hutzinger, O.; Safe, S.; Zitko, V. "The Chemistry of PCB's"; CRC Press: Cleveland, Ohio, 1974. Furukawa, K . ; Matsumura, F. J. Agr. Food Chem. 1976, 24, 25156. Clark, R.R.; Chian, E.S.K.; Griffin, R.A. Appl. Env. Microbiol. 1979, 37, 680-85. Tucker, E . S . ; Saeger, V.W.; Hicks, O. B. Env. Contam. Tox. 1975, 14, 705-13. Brown, J.F., J r . ; Wagner, R.E.; Bedard, D . L . ; Brennan, M . J . ; Carnahan, J.C.; May, R.J.; Tofflemire, T . J . Northeastern Environmental Science 1984, 3, 167-179. Van Vleet, E . S . ; Quinn, J.G. J. Fish. Res. Board Can. 1978, 35, 536-43. Cranwell, P.A. Org. Geochem. 1981, 3, 79-89. Boehm, P.D.; Quinn, J.G. Est. Coast. Mar. S c i . 1978, 6, 741-94. Farrington, J.W.; Quinn, J.G. Est. Coast. Mar. S c i . 1973, 1, 71-79. Simoneit, B.R.T.; Kaplan, I.R. Mar. Env. Research 1980, 3, 113128. Eglinton, G.; Hamilton, R.J. Science 1967, 156, 1322-1335. Simoneit, B.R.T. In "Chemical Oceanography"; Riley, J.P.; Chester, R., Eds.; Academic Press: N.Y., 1978; V o l . 7, Chap. 39, pp. 233-311. Smith, D . J . ; Eglinton, G.; Morris, R.J. Gecochim. Cosmochim. Acta 1983, 47, 2225-2232. Thompson, S.; Eglinton, G. Geochim. Cosmochim. Acta 1978, 42, 199-207. Buhler, D.R.; Rasmusson, M.E.; Nakaue, H.S. Env. S c i . & Tech. 1973, 7, 929-34. M i l l e r , Α., III; Henderson, M.C.; Buhler, D.R. Molecular Pharmacol. 1978, 14, 323-36.


214

ORGANIC MARINE GEOCHEMISTRY

54. Mathur, S.P.; Morley, H.V. B. Env. Contam. Tox. 1978, 20, 26874. 55. Sims, J.L.; Pfaender, F.K. B. Env. Contam. Tox. 1975, 14, 21420. 56. Lee, R.F.; Ryan, C. Proc. Workshop: Microbial Degradation Pollut. Mar. Envi., 1979, pp. 443-50. EPA-600/9-79-012. 57. Murthy, N.B.K.; Kaufman, D.D.; Fries, G.F. J . Env. Sci. Health 1979, B14, 1-14.


RECEIVED September 16, 1985


Organic Marine Geochemistry - American Chemical Society

Recommend Documents