title: Assessing bioavailability of DDT and metabolites in marine sediments using solid-phase microextraction with performance reference compounds.
abstract: Solid-phase microextraction (SPME) has often been used to estimate the freely dissolved concentration (Cfree ) of organic contaminants in sediments. A significant limitation in the application of SPME for Cfree measurement is the requirement for attaining equilibrium partition, which is often difficult for strongly hydrophobic compounds such as DDT. A method was developed using SPME with stable isotope-labeled analogues as performance reference compounds (PRCs) to measure Cfree of DDT and metabolites (DDTs) in marine sediments. Six (13) C-labeled or deuterated PRCs were impregnated into polydimethylsiloxane (PDMS) fiber before use. Desorption of PRCs from PDMS fibers and absorption of DDTs from sediment were isotropic in a range of sediments evaluated ex situ under well-mixed conditions. When applied to a historically contaminated marine sediment from a Superfund site, the PRC-SPME method yielded Cfree values identical to those found by using a conventional equilibrium SPME approach (Eq-SPME), whereas the time for mixing was reduced from 9 d to only 9 h. The PRC-SPME method was further evaluated against bioaccumulation of DDTs by Neanthes arenaceodentata in the contaminated sediment with or without amendment of activated carbon or sand. Strong correlations were consistently found between the derived equilibrium concentrations on the fiber and lipid-normalized tissue residues for DDTs in the worms. Results from the present study clearly demonstrated the feasibility of coupling PRCs with SPME sampling to greatly shorten sampling time, thus affording much improved flexibility in the use of SPME for bioavailability evaluation.
authors: Department of Environmental Science, University of California, Riverside, CA, USA. lyla.bao@ucr.edu
authors: Lian-Jun
authors: LJ
authors: Bao
authors: Fang
authors: F
authors: Jia
authors: J
authors: J
authors: Crago
authors: Eddy Y
authors: EY
authors: Zeng
authors: D
authors: D
authors: Schlenk
authors: Jay
authors: J
authors: Gan
mesh_terms: D000818:Animals; D059001:Aquatic Organisms; D001711:Biotransformation; D002247:Carbon Isotopes; D003634:DDT / Q000032:analysis* / Q000378:metabolism; D003903:Deuterium; D004129:Dimethylpolysiloxanes; D019015:Geologic Sediments / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D011077:Polychaeta / Q000378:metabolism; D012015:Reference Standards; D052617:Solid Phase Microextraction / Q000592:standards
chemical_list: D002247:Carbon Isotopes; D004129:Dimethylpolysiloxanes; C013830:baysilon; D003903:Deuterium; D003634:DDT
keywords: Bioavailability; DDT; Passive sampling; Performance reference compound; Solid-phase microextraction (SPME)
references: Environ Toxicol Chem. 2009 Apr;28(4):733-40
references: 19391690
references: Environ Sci Technol. 2009 Dec 1;43(23):8888-94
references: 19943662
references: Chemosphere. 2008 Aug;72(10):1435-1440
references: 18597813
references: Anal Chem. 2004 Oct 1;76(19):5807-15
references: 15456301
references: Environ Sci Technol. 2003 Jan 15;37(2):268-74
references: 12564897
references: Environ Pollut. 2009 Apr;157(4):1382-7
references: 19117651
references: Anal Chem. 2009 Nov 15;81(22):9472-80
references: 19908907
references: Environ Sci Technol. 2012 Jan 17;46(2):937-44
references: 22201472
references: Environ Sci Technol. 2009 May 15;43(10):3757-63
references: 19544884
references: Environ Toxicol Chem. 2008 Mar;27(3):499-508
references: 18516795
references: Chemosphere. 2008 Mar;71(2):337-44
references: 17942136
references: Environ Sci Technol. 2008 Aug 15;42(16):6086-91
references: 18767670
references: Environ Sci Technol. 2004 Oct 15;38(20):5458-64
references: 15543751
references: Chemosphere. 2009 Jan;74(4):522-9
references: 19000629
references: Environ Sci Technol. 2007 Jun 1;41(11):4026-31
references: 17612185
references: J Chromatogr A. 2005 Feb 25;1066(1-2):165-75
references: 15794568
references: Environ Toxicol Chem. 2004 Nov;23(11):2551-62
references: 15559268
references: Environ Toxicol Chem. 2007 Oct;26(10):2143-50
references: 17867891
references: Environ Sci Technol. 2011 May 1;45(9):4053-9
references: 21473574
references: Environ Sci Technol. 2003 Sep 15;37(18):4213-20
references: 14524455
references: Environ Sci Technol. 2011 Oct 1;45(19):8437-43
references: 21846112
references: J Chromatogr A. 2006 May 26;1116(1-2):240-7
references: 16580005
references: Environ Sci Technol. 2009 Apr 15;43(8):2865-70
references: 19475963
references: Environ Pollut. 2012 Aug;167:34-40
references: 22522316
references: Environ Sci Technol. 2010 Sep 15;44(18):6917-25
references: 20726511
references: Environ Sci Technol. 2012 Feb 21;46(4):2413-9
references: 22316215
references: Integr Environ Assess Manag. 2005 Jan;1(1):2-8
references: 16637142
references: Environ Sci Technol. 2007 Feb 15;41(4):1317-23
references: 17593736
references: Environ Sci Technol. 2009 Mar 1;43(5):1430-6
references: 19350915
references: Environ Sci Technol. 2008 Feb 15;42(4):1332-6
references: 18351113
references: Environ Sci Technol. 2005 Apr 15;39(8):2880-7
references: 15884389