University of Nebraska - Lincoln DigitalCommons@University of Nebraska - Lincoln USGS Staff -- Published Research US Geological Survey 2002 Review of the background and application of triolein-containing semipermeable membrane devices in aquatic environmental study Yibing Lu Research Center for Eco-Enironmental Sciences Zijian Wang Research Center for Eco-Enironmental Sciences, [email protected] James Huckins Columbia Enironmental Research Center, [email protected] Follow this and additional works at: https://digitalcommons.unl.edu/usgsstaffpub Lu, Yibing; Wang, Zijian; and Huckins, James, "Review of the background and application of triolein- containing semipermeable membrane devices in aquatic environmental study" (2002). USGS Staff -- Published Research. 552. https://digitalcommons.unl.edu/usgsstaffpub/552 This Article is brought to you for free and open access by the US Geological Survey at DigitalCommons@University of Nebraska - Lincoln. It has been accepted for inclusion in USGS Staff -- Published Research by an authorized administrator of DigitalCommons@University of Nebraska - Lincoln. Aquatic Toxicology 60 (2002) 139–153 www.elsevier.com/locate/aquatox Review Review of the background and application of triolein-containing semipermeable membrane devices in aquatic environmental study Yibing Lu a, Zijian Wang a,*, James Huckins b a State Key Laboratory of En6ironmental Aquatic Chemistry, Research Center for Eco-En6ironmental Sciences, Beijing 100085, China b Columbia En6ironmental Research Center, USGS, Columbia, MO, USA Received 5 March 2002; accepted 15 April 2002 Abstract This paper briefly reviews research on passive in situ samplers for aquatic environments but focuses on the development and application of the triolein-containing semipermeable membrane device in aquatic environmental monitoring. Special attention is paid to the calibration of the devices, quality control issues, and its potential uses in environmental assessments of aquatic contaminants. Also, the suitability of the technique for incorporation with selected bioassays is examined. © 2002 Elsevier Science B.V. All rights reserved. Keywords: Review; Triolein-semipermeable membrane device; Calibration; QA/QC; Applications 1. Introduction Nearly all-environmental samples require some type of preparation before analysis. Conventional Chemicals listed by the US EPA as priority solid phase extraction (SPE), such as XAD resin pollutants contribute little to broad environmen- sorption, and liquid–liquid extraction are among tal indices such as BOD, COD or TOC. Never the oldest and most frequently used sample the less, these contaminants can pose a major preparation methods. However, use of these threat to ecosystem and human health. For exam- methods for monitoring ultra trace to trace-level ple, many substances that cause cancer belong to (e.g. pg to ng/L) organic contaminants in water, persistent organic contaminants (POPs). In 1999, may be problematic. More specifically, difficulties the China EPA designated 40-organic contami- or limitations associated with the methods are nants from US EPA’s list of 2347 toxic chemicals often encountered when collecting and extracting as priority pollutants for water quality standards. large volumes of water needed for trace contami- nant analysis. These include sampling and han- * Corresponding author. Tel.: +86-10-62849140; fax: +86- 10-6292-3563. dling induced changes in some water quality E-mail address: [email protected] (Z. Wang). parameters, and loss of analytes due to filtration, 0166-445X/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved. PII: S0166-445X(02)00056-5 140 Y. Lu et al. / Aquatic Toxicology 60 (2002) 139–153 volatilization and sorption. Also, analysis of ex- Several passive samplers have been proposed cised water reflects residue composition only at based on the diffusion of hydrophobic substances the moment of sampling and may fail to detect from the water to membrane bags filled with episodic contamination events (Huckins et al., lipophilic phases. Some of the early designs in- 1990a, 1993). Therefore, the recent availability of cluded dialysis bags made of regenerated cellulose SPE cartridges has facilitated the analysis of tubing and polyethylene membrane bags filled many environmental samples, but the method is with hexane (Sodergren, 1987, 1990; Johnson, generally more suitable for the analysis of samples 1991; Hasset et al., 1989). At about the same time, with moderate (e.g. mg/L) to trace levels of target Zabik (1988) and Huckins (1988) evaluated contaminants. polypropylene, polyvinyl chlorides, polyacetate, Because of the aforementioned difficulties in and silicone membranes for use in passive sam- analyzing trace-level contaminants, the levels of plers. In other studies (Byrne and Aylott, 1980), POPs in water are often inferred from their equi- vinyl chlorides, polyvinylidene fluoride, polyte- librium concentrations in the tissue of aquatic trafluoro ethylene, acrylic copolymer and nylon organisms. Weaknesses in this approach include membrane bags were used as semipermeable possible metabolism and depuration of accumu- membranes for passive samplers. Also, lated chemicals, prejudices in absorption, site-to- polyethylene membranes were filled with XAD-4 site variations in organism stress, and limited and C18, or common organic solvents such as viability (Prest et al., 1995b), which affect equi- 2,2,4-trimethylpentane, octanol, and hexane for librium concentrations. Estimates of POP concen- environmental sampling (Zabik et al., 1992). trations in water can also be made by measuring Pekol and Cox (1995) described a system in which their concentrations in benthic sediments from micellar Brij35 and Brij58 were used in combina- rivers, lakes or seashores and then using equi- tion with a cellulose ester dialysis membrane. The librium distribution coefficients (i.e. Kocs) to micellar media compared well with organic sol- derive levels of dissolved phase analytes (Gale et vents as receivers for fugacity based membrane al., 1997). This approach is limited by the assump- preconcentrators of hydrophobic compounds. In tion of equilibrium between sediments and the a comparative study (Macrae and Hall, 1998), water column, and the potential effects of organic triolein-containing semipermeable membrane carbon quality differences among sediments that device (triolein-SPMD), Tenax TA, and are not accounted for in current equilibrium parti- polyethylene tube dialysis (PTD) of sediment were tion models. used to estimate the available fraction of poly- Increasingly, the development of effective, eco- cyclic aromatic hydrocarbons (PAHs) in marine nomic and selective passive sampling techniques is sediment slurries. The results of this study sug- becoming a widespread goal of environmental gested that PTD is useful for assessing chemical scientist. In particular there is a need for tech- exposure from to soils or sediments, while tri- niques, which fulfill the demands of monitoring olein-SPMD and Tenax TA are useful for estima- trace or ultra-trace bioavailable organic contami- tion of the fraction of chemicals in sediments that nants in water and at the same time bridge the would likely be biodegradable in reasonable gaps between environmental analytical chemistry length of time. and ecotoxicology approaches. Among various Recently a polar organic chemical integrative passive sampling approaches for organic contami- sampler (POCIS), consisting of a hydrophilic nants, the solid phase micro-extraction (SPME) polyethersulfone membrane containing an admix- fibers and semipermeable membrane devices (SP- ture of a hyper-cross linked polystyrene-divinyl- MDs) appear to show the most promise. SPME benzene SPE resin and S-X3 Biobeads coated with fibers are widely accepted as analytical tools for fine particles of dispersed Ambersorb® 1500, was measuring semi-volatile contaminants (Pawliszyn, designed (Alvarez et al., 2000). The polyethersul- 1997), are very convenient to use, but are gener- fone membrane was selected because of all the ally limited by small sample size/capacity. membranes studied; it exhibited the greatest up- Y. Lu et al. / Aquatic Toxicology 60 (2002) 139–153 141 take of hydrophilic analytes and had the greatest thermal motions of the polymer chains form tran- membrane durability. Using POCIS samplers, lin- sient cavities with maximum diameters of approx- ear uptake of polar analytes (e.g. atrazine) was imately 10 A,(Huckins et al., 1990a). Because the observed through 28 days, and biofouling was cross-sectional diameters of most environmental minimal. contaminant molecules are nearly as large as LDPE Besides SPME fibers, the most popular passive cavities, only dissolved (i.e. readily bioavailable) sampling configuration for aquatic environments is organic contaminants can diffuse into the mem- the triolein-containing SPMD developed by Huck- brane and be concentrated in the membrane and ins (1988) and Huckins et al. (1990a). Fig. 1 triolein. The neutral-triglyceride triolein was se- illustrates the principle of the triolein-SPMD. The lected for use in SPMDs for the following reasons: following sections summarize the theory, practice, (1) it is a significant constituent of fish lipids; (2) and applications of SPMDs as passive in situ Chiou (1985) has shown a good correlation between samplers of aquatic environments. equilibrium triolein–water partition coefficients (Ktws) and widely available equilibrium octanol– water partition coefficients (Kows); (3) the high 2. Design and basis