Jimmie D. Petty

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.

An expanded approach to the study and measurement of PCBs and selected planar halogenated aromatic environmental pollutants.

Analysis of environmental polychlorinated biphenyl (PCB) residues is complicated by the presence of a large number of congeners in the various commercial mixtures. Currently, environmental levels of PCBs are often reported i n terms of total PCB concentration or Aroclora content. Marked differences exist in the toxicity of individuals chlorobiphenyls and impurities in technical PCB mixtures..2 To predict adequately the environmental hazards associated with PCB pollution, detailed information is required on the composition of technical PCB mixtures and environmental PCB residues. Assessment of the biologic significance of environmental PCB residues necessitates the establishment of definitive relationhhips between PCB structure and toxicity. Recent studies by Goldstein et a/ and Poland et al. indicate that PCB components lacking 0.0-Chlorine (CI) substitution and having four or more CI atoms, may account for a significant portion of the toxicologic activity resulting from acute exposures to PCB mixtures. To date, use of high resolution (HR) wall-coated open tubular (WCOT) glass capillary gas chromatographic (GC) columns has provided the most complete separation of PCB congeners in technical mixture^..^ Earlier, we found that 28M WCOT glass capillary C87,5 Apiezon-L and SE-30 columns failed to resolve PCBs lacking o,o-CI substitution from several other components present in Aroclors I248 and 1254.4 However, application of PX-21 carbon or PX-21 carbon/foam column chromatography6 provided separations adequate for the quantitation of non-o,oClsubstituted PCBs and trace planar impurities in technical m i x t u r e ~ . ~ The retention volumes of PCB components on carbon columns generally increased with decreasing o,o-CI substitution and with meta and para CI substitution. Large volumes of toluene were required to elute planar non-0.0-substituted PCBs, chlorinated dibenzofurans, and dioxins from granular (>325 mesh) PX-21 carbon columns. Use of small amounts of PX-21 carbon on foam as an adsorbent for the isolation of these compounds permitted a significant reduction in the solvent required. We report the carbon separation of Aroclor 1248 into four fractions to determine the toxicity of structurally related PCB components to fish. PCB components in each fraction were characterized using HRGC 28M WCOT glass capillary columns of Apiezon-L. and Cg, hydrocarbon. Rainbow trout (Salmo gairdncri) were exposed to Aroclor 1248 fractions containing 1 4 0.0-CI for 28 days with no visible effects a t

Modular containers for microcosm and process model studies on the fate and effects of aquatic contaminants

Abstract Container modules are described for the laboratory simulation of selected processes and ecosystems that are representative of lentic environments. Emphasis is placed on design features permitting mass balance accountability of contaminant residues and procedural cautions required for the proper use of the described systems in environmental simulations. Experiments on the efficiency of container modules for microbial mineralization studies were conducted using 14 CNaHCO 3 , and acidification resulted in a 14 CCO 2 recovery of 97.3 ± 4.7% ( x ± SD ) . The trapping efficiency of pesticides volatilized from water and glass surfaces was investigated using the same module and the mean recoveries of 14 C-fonofos and 14 C-trifluralin were 114.2 ± 3.2% and 95.2 ± 3.5%, respectively. The mass balance capabilities of the system was also demonstrated for extended microcosm exposures to 14 C-trifluralin.

Use of the Semipermeable Membrane Device (Spmd) to Sample Polycyclic Aromatic Hydrocarbon Pollution In A Lotic System

Abstract Relative concentrations of aqueous polycyclic aromatic hydrocarbons (PAH) were investigated in an urban creek. Samples were obtained at five sites within a 600-m segment of the creek that is critical habitat for an endangered species of fish. the sampling technique entailed immersion of semipermeable membrane devices (SPMDs) in the water for intervals as long as 64 d. SPMDs are passive, in situ, mtegrative samplers of bioavailable (truly dissolved) PAH and other hydrophobic organic contaminants. Two point sources of PAH to the 600-m segment of the creek were differentiated. Aqueous concentrations were found to wane dramatically over the relatively short section of the creek between the point sources. All samples were almost devoid of alkyl-substituted PAH, indicating that the ultimate sources were probably of pyrogenic nature.

Dynamics of purified and industrial pentachlorophenol in fathead minnows

Fathead minnows (Pimephales promelas) were exposed to purified and industrial composite pentachlorophenol (PCP, 50 Μg/L) for 31 days in flowthrough diluter systems and then placed in fresh water for an elimination phase. Whole body residues were analyzed for PCP and its degradation products through time. Pentachlorophenyl-Β-glucuronide and pentachloroanisole were detected in fish tissues. Residues of PCP plateaued in fish from both experiments before the end of the 31-day exposure. Fish exposed to industrial composite and purified PCP concentrated PCP residues by 284 and 174 times, respectively. On an average, pentachlorophenyl-Β-glucuronide residues were lower in fish exposed to the industrial composite.

Fate and metabolism of isopropylphenyl diphenyl phosphate in freshwater sediments.

Ames, B. N.; McCann, J.; Yamasaki, E. Mutat. Res. 1975, 31. 347-364. Tokiwa, H.; Nakagawa, R.; Ohnishi, Y. Mutat. Res. 1981, 91, 321-325. Graham, S. C.; Homer, J. B.; Rosenfeld, J. L. J. Proc. R. SOC. London, Ser. A 1975, 344,259-285. Handbook of Chemistry and Physics, 47th ed.; Chemical Rubber Co.: Cleveland, OH, 1967. Schuetzle, D.; Riley, T. C.; Prater, T. J.; Harvey, T. M.; Hunt, D. F. Anal. Chem. 1981,54, 265-271. Schuetzle, D. paper presented at the EPA Symposium on the Application of Short-Term Bioassays in the Analysis of Complex Environmental Mixtures, Chapel Hill, NC, Jan

Collection and detection of lipophilic chemical contaminants in water, sediment, soil, and air—SPMD-TOX

This toxicological screening tool is a method designed to collect and detect the presence of toxic lipophilic chemical contaminants in water, sediment, soil, and air. This method is applicable to the following types of samples: (1) surface water, groundwater or wastewater; (2) sediment or pore water; (3) soil; and (4) air. A pasive sorptive tool, known as the semipermeable membrane device (SPMD), collects lipophilic chemical contaminants from water, sediment, soil, and air and a short-term, microscale in vitro procaryotic assay known as the Microtox acute basic test assay (Microtox®, Azur Environmental, Carlsbad, CA), detect accumulated toxins.

Presence and Potential Significance of o-o’-Unsubstituted PCB Isomers and Trace Aroclor® 1248 and 1254 Impurities

Determination of the potential impact of PCB contamination on aquatic ecosystems is facilitated by information on the toxico-logical significance of specific PCB constituents. In support of this approach, recent studies, (Goldstein et al 1977 and Poland and Glover 1977), indicate that physiological activity associated with the technical PCB mixtures may be largely due to the presence of trace levels of PCB isomers having no o-o’-chlorine substitution. Hepatic enzyme induction from exposure to the most active of these isomers may approach that of the chlorinated-dibenzofurans and -dioxins. Separation and isolation techniques for structurally similar components of Aroclor1/ mixtures are prerequisites for structure-toxicity correlation studies.

Approaches to Comprehensive Analyses of Persistent Halogenated Environmental Contaminants

A series of chromatographic processes has been integrated into an automated sequential procedure that has been specifically developed for uninterrupted purification and fractionation of multiclass organic chemical residues from environmental samples. The effectiveness and general applicability of this sequential cleanup and fractionation procedure were demonstrated by the recovery of 39 chemicals representing a broad range of residue classes from a fortified fish sample. A chromatographic controller under construction is designed to carry out the numerous sample and solvent manipulations in an automated and continuous procedure. Alkali metal hydroxide treated silica gel effectively separated phenols and acids from neutral compounds.

Distribution and rate of disappearance of fluorene in pond ecosystems

Fluorene, an energy related polynuclear aromatic hydrocarbon, was applied to several experimental pond ecosystems to effect concentrations of 0.12, 0.5, 2.0, 5.0, and 10.0 mg/L. Water, benthic sediment, and rooted macrophytes were monitored for fluorene residues for 56 days after application. Most of the fluorene at concentrations greater than its water solubility appeared to sublime from the surface of the ponds. The rate of disappearance of fluorene from the water decreased as the application rate increased. This reduction was linked to high concentrations and a flux of fluorene from benthic sediments, macrophytes, and pond surfaces to water columns. Several parameters of photosynthetic primary production were statistically linked to the accelerated disappearance of fluorene from the water.