Purification of triolein for use in semipermeable membrane devices (SPMDs).

Analyses of triolein-containing semipermeable membrane devices (SPMDs) have sometimes been impeded by interferences caused by impurities endemic to triolein that codialyze with the analytes. Oleic acid and methyl oleate have been the most troublesome of these impurities because of their relatively high concentrations in triolein and because significant residues of both can persist even after size exclusion chromatographic (SEC) fractionation. These residues have also been blamed for false-positive signals during bioindicator testing of SPMD dialysates. To prevent these problems, a simple, cost-effective procedure was developed for purifying triolein destined for use in SPMDs: the bulk triolein is repeatedly (6x) partitioned against methanol. Tests of the procedure show that 14C-oleic acid is completely removed from the triolein. After SEC fractionation, dialysates of standard-size SPMDs made with the purified triolein contain less than 5 microg of methyl oleate as compared to sometimes more than 500 microg for dialysates (also after SEC) of SPMDs made with unpurified triolein. Gas chromatographic analyses with flame ionization and electron capture detection show that the purification treatment also greatly reduces the number and size of peaks caused by unidentified contaminants in the triolein. Microtox basic assay of dialysates of SPMDs shows that those made with the purified triolein have lower acute toxicities than dialysates of SPMDs made with unpurified triolein. Yeast estrogen screen (YES) testing of SPMDs fabricated with unpurified and purified triolein demonstrates that the purification process removes all background estrogenic activity.

A holistic passive integrative sampling approach for assessing the presence and potential impacts of waterborne environmental contaminants.

As an integral part of our continuing research in environmental quality assessment approaches, we have developed a variety of passive integrative sampling devices widely applicable for use in defining the presence and potential impacts of a broad array of contaminants. The semipermeable membrane device has gained widespread use for sampling hydrophobic chemicals from water and air, the polar organic chemical integrative sampler is applicable for sequestering waterborne hydrophilic organic chemicals, the stabilized liquid membrane device is used to integratively sample waterborne ionic metals, and the passive integrative mercury sampler is applicable for sampling vapor phase or dissolved neutral mercury species. This suite of integrative samplers forms the basis for a new passive sampling approach for assessing the presence and potential toxicological significance of a broad spectrum of environmental contaminants. In a proof-of-concept study, three of our four passive integrative samplers were used to assess the presence of a wide variety of contaminants in the waters of a constructed wetland, and to determine the effectiveness of the constructed wetland in removing contaminants. The wetland is used for final polishing of secondary-treatment municipal wastewater and the effluent is used as a source of water for a state wildlife area. Numerous contaminants, including organochlorine pesticides, polycyclic aromatic hydrocarbons, organophosphate pesticides, and pharmaceutical chemicals (e.g., ibuprofen, oxindole, etc.) were detected in the wastewater. Herein we summarize the results of the analysis of the field-deployed samplers and demonstrate the utility of this holistic approach.

Comparisons of coarse and fine versions of two carbons for reducing the bioavailabilities of sediment-bound hydrophobic organic contaminants.

Coarse (whole) and finely ground Ambersorb 1500 and coarse and fine coconut charcoal were compared as to their efficiencies in scavenging organic contaminants desorbed from sediment. Aqueous slurries of a test sediment spiked (1 ppm) with p,p(')-DDE (DDE), 2,2('),5,5(')-tetrachlorobiphenyl (TCB), naphthalene (NAP), or phenanthrene (PHEN), and containing 1% levels of the test carbons were treated by shaking at 35 degrees C while exposed to clusters of low-density polyethylene membrane (detox spiders). Controls consisted of spiked sediments and detox spiders but no added carbon of any kind and thus represented unimpeded bioavailabilities (to the spiders). After the treatments--agitation periods from 2.5 to 60 h, depending on contaminant hydrophobicity--the exposed detox spiders were analyzed. The fine carbon of either type was more effective than its coarser variant in obstructing contaminant bioavailabilities. The finer variants of both carbons obstructed the bioavailabilities of NAP and PHEN equally well as did the coarser variants of both. Whole Ambersorb 1500 and coarse coconut charcoal were similarly ineffective in intercepting TCB and DDE. Ground Ambersorb 1500 obstructed virtually all bioavailability of all four contaminants and was far more effective than fine coconut charcoal in intercepting DDE and TCB. An additional experiment compared the effectiveness of ground Ambersorb 1500 and fine coconut charcoal in obstructing the bioavailabilities from sediment of a broad array of spiked organochlorine pesticides. The performance of ground Ambersorb 1500 was again found to be superior; the bioavailable levels of each of the 27 pesticides were markedly lower in the presence of ground Ambersorb 1500 than in the presence of fine coconut charcoal.

An approach for assessment of water quality using semipermeable membrane devices (SPMDs) and bioindicator tests.

As an integral part of our continued development of water quality assessment approaches, we combined integrative sampling, instrumental analysis of widely occurring anthropogenic contaminants, and the application of a suite of bioindicator tests as a specific part of a broader survey of ecological conditions, species diversity, and habitat quality in the Santa Cruz River in Arizona, USA. Lipid-containing semipermeable membrane devices (SPMDs) were employed to sequester waterborne hydrophobic chemicals. Instrumental analysis and a suite of bioindicator tests were used to determine the presence and potential toxicological relevance of mixtures of bioavailable chemicals in two major water sources of the Santa Cruz River. The SPMDs were deployed at two sites; the effluent weir of the International Wastewater Treatment Plant (IWWTP) and the Nogales Wash. Both of these systems empty into the Santa Cruz River and the IWWTP effluent is a potential source of water for a constructed wetland complex. Analysis of the SPMD sample extracts revealed the presence of organochlorine pesticides (OCs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). The bioindicator tests demonstrated increased liver enzyme activity, perturbation of neurotransmitter systems and potential endocrine disrupting effects (vitellogenin induction) in fish exposed to the extracts. With increasing global demands on limited water resources, the approach described herein provides an assessment paradigm applicable to determining the quality of water in a broad range of aquatic systems.

Considerations involved with the use of semipermeable membrane devices for monitoring environmental contaminants.

Semipermeable membrane devices (SPMDs) are used with increasing frequency, and throughout the world as samplers of organic contaminants. The devices can be used to detect a variety of lipophilic chemicals in water, sediment/soil, and air. SPMDs are designed to sample nonpolar, hydrophobic chemicals. The maximum concentration factor achievable for a particular chemical is proportional to its octanol-water partition coefficient. Techniques used for cleanup of SPMD extracts for targeted analytes and for general screening by full-scan mass spectrometry do not differ greatly from techniques used for extracts of other matrices. However, SPMD extracts contain potential interferences that are specific to the membrane-lipid matrix. Procedures have been developed or modified to alleviate these potential interferences. The SPMD approach has been demonstrated to be applicable to sequestering and analyzing a wide array of environmental contaminants including organochlorine pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polychlorinated dioxins and dibenzofurans, selected organophosphate pesticides and pyrethroid insecticides, and other nonpolar organic chemicals. We present herein an overview of effective procedural steps for analyzing exposed SPMDs for trace to ultra-trace levels of contaminants sequestered from environmental matrices.