Evaluation of the use of performance reference compounds in an Oasis-HLB adsorbent based passive sampler for improving water concentration estimates of polar herbicides in freshwater.

Passive samplers such as the Polar Organic Chemical Integrative Sampler (POCIS) are useful tools for monitoring trace levels of polar organic chemicals in aquatic environments. The use of performance reference compounds (PRC) spiked into the POCIS adsorbent for in situ calibration may improve the semiquantitative nature of water concentration estimates based on this type of sampler. In this work, deuterium labeled atrazine-desisopropyl (DIA-d5) was chosen as PRC because of its relatively high fugacity from Oasis HLB (the POCIS adsorbent used) and our earlier evidence of its isotropic exchange. In situ calibration of POCIS spiked with DIA-d5 was performed, and the resulting time-weighted average concentration estimates were compared with similar values from an automatic sampler equipped with Oasis HLB cartridges. Before PRC correction, water concentration estimates based on POCIS data sampling rates from a laboratory calibration exposure were systematically lower than the reference concentrations obtained with the automatic sampler. Use of the DIA-d5 PRC data to correct POCIS sampling rates narrowed differences between corresponding values derived from the two methods. Application of PRCs for in situ calibration seems promising for improving POCIS-derived concentration estimates of polar pesticides. However, careful attention must be paid to the minimization of matrix effects when the quantification is performed by HPLC-ESI-MS/MS.

Semivolatile organic compounds in residential air along the Arizona-Mexico border.

Concerns about indoor air quality and the potential effects on people living in these environments are increasing as more reports about the toxicities and the potential indoor air exposure levels of household-use chemicals and chemicals from housing and fumishing manufacture in air are being assessed. Gas chromatography/mass spectromery was used to confirm numerous airborne contaminants obtained from the analysis of semipermeable membrane devices deployed inside of 52 homes situated along the border between Arizona and Mexico. We also describe nontarget analytes in the organochlorine pesticide fractions of 12 of these homes; this fraction is also the most likely to contain the broadest scope of bioconcentratable chemicals accumulated from the indoor air. Approximately 400 individual components were identified, ranging from pesticides to a wide array of hydrocarbons, fragrances such as the musk xylenes, flavors relating to spices, aldehydes, alcohols, esters and phthalate esters, and other miscellaneous types of chemicals. The results presented in this study demonstrate unequivocally that the mixture of airborne chemicals present indoors is far more complex than previously demonstrated.

Comparison of the uptake of polycyclic aromatic hydrocarbons and organochlorine pesticides by semipermeable membrane devices and caged fish (Carassius carassius) in Taihu Lake, China.

Uptake of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) by triolein-containing semipermeable membrane devices (SPMDs) and by crucian carp (Carassius carassius) was studied in Taihu Lake, a shallow, freshwater lake in China. Crucian carp and SPMDs were deployed side by side for 32 d. The first-order uptake rate constants of individual PAHs and OCPs for the two matrices were calculated and compared to relate the amounts of chemicals accumulated by the matrices to dissolved water concentrations. On a wet-weight basis, total concentrations of PAHs and OCPs in crucian carp fillets averaged 49.5 and 13.6 ng/g, respectively, after the 32-d exposure, whereas concentrations in whole SPMDs averaged 716.9 and 62.3 ng/g, respectively. The uptake rate constants of PAHs and OCPs by SPMDs averaged seven- and fivefold higher, respectively, than those for crucian carp; however, the patterns of uptake rate constants derived from test chemical concentrations in the crucian carp and SPMDs were similar. Although equilibrium was not reached for some PAHs and OCPs during the 32-d exposure period, a reasonably good correlation between the concentration factors (CFs) and octanol/water partition coefficient (Kow) values of PAHs and OCPs in SPMDs (r = 0.86, p < 0.001) was observed when potential sorption to dissolved organic carbon was taken into account. Similar efforts to correlate the CFs and Kow values of PAHs and OCPs in crucian carp (r = 0.75, p < 0.001) were less successful, likely because of PAH metabolism by finfish. Overall, the present results suggest that SPMDs may serve as a surrogate for contaminant monitoring with fish in freshwater lake environments.

Photodegradation of polyaromatic hydrocarbons in passive air samplers: field testing different deployment chambers.

Semi-permeable membrane devices (SPMDs) were loaded with deuterated anthracene and pyrene as performance reference compounds (PRCs) and deployed at a test site in four different chambers (open and closed box chamber, bowl chamber and cage chamber) for 29 days. The losses of PRCs and the uptake of polyaromatic hydrocarbons (PAHs) from the ambient air were quantified. UV-B levels measured in each deployment chamber indicated that SPMDs would be exposed to the most UV-B in the cage chamber and open box chamber. Significantly less PAHs were quantified in SPMDs deployed in the cage chamber and open box chamber compared to samplers from the other two chambers, suggesting that photodegradation of PAHs had occurred. The loss of PRCs confirmed these results but also showed that photodegradation was occurring in the closed box chamber. The bowl chamber appears to provide the best protection from the influence of direct photodegradation.

Use of powdered coconut charcoal as a toxicity identification and evaluation manipulation for organic toxicants in marine sediments.

We report on a procedure using powdered coconut charcoal to sequester organic contaminants and reduce toxicity in sediments as part of a series of toxicity identification and evaluation (TIE) methods. Powdered coconut charcoal (PCC) was effective in reducing the toxicity of endosulfan-spiked sediments by 100%. Powdered coconut charcoal also was effective in removing almost 100% of the toxicity from two field sediments contaminated with polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). Powdered coconut charcoal did not change the toxicity of ammonia or metal-spiked sediments; however, there was some quantitative reduction in the concentrations of free metals (element specific) in metal-spiked sediments. Powdered coconut charcoal is an effective, relatively specific method to sequester and remove toxicity from sediments contaminated with organic contaminants.

Assessing the toxicity and teratogenicity of pond water in north-central Minnesota to amphibians.

BACKGROUND: Incidence of amphibian deformities have increased in recent years, especially in the northern region of the United States. While many factors have been proposed as being responsible for generating deformities (e.g., contaminants, ultraviolet radiation [UV], parasites), no single cause has been definitively established. METHODS: To determine whether waterborne chemicals are responsible for amphibian deformities in ponds in north-central Minnesota, we deployed semipermeable membrane devices (SPMDs) in an impacted and a reference site to accumulate lipophilic contaminants. We then exposed native tadpoles (northern leopard frogs; Rana pipiens) to the SPMD extracts combined with two agricultural pesticides (atrazine, carbaryl) at two levels of UV radiation. RESULTS AND DISCUSSION: UV radiation alone caused a slight increase in hatching success and tadpole growth rate. Deformity rate among hatchlings was high following exposure to SPMD extracts from the reference site in the absence of UV, suggesting that chemicals present at this site are broken down by UV to less harmful forms, or become less bioavailable. Conversely, impacted site SPMD extracts caused hatchling deformities only in the presence of UV, suggesting that UV potentiates the teratogenicity of the compounds present there. Impacted site SPMD extracts significantly increased the number of bony triangles among metamorphs, a common deformity observed at this site. The incidence of skin webbings increased significantly with SPMD extracts from both sites as well as with our pesticide control containing atrazine and carbaryl alone. CONCLUSIONS: Higher deformity rates among tadpoles reared in the presence of UV radiation and SPMD extracts from sites where deformities are common indicates a chemical compound (or compounds) in the water at this site may be causing the deformities. RECOMMENDATIONS AND OUTLOOK: It is important to examine the effects of chemical stressors in the presence of other natural stressors (e.g., UV radiation) to gain a better understanding of how multiple stressors work to impact amphibians and amphibian populations.

Compound-specific carbon and hydrogen isotope analysis of sub-parts per billion level waterborne petroleum hydrocarbons.

Compound-specific carbon and hydrogen isotope analysis (CSCIA and CSHIA) has been increasingly used to study the source, transport, and bioremediation of organic contaminants such as petroleum hydrocarbons. In natural aquatic systems, dissolved contaminants represent the bioavailable fraction that generally is of the greatest toxicological significance. However, determining the isotopic ratios of waterborne hydrophobic contaminants in natural waters is very challenging because of their extremely low concentrations (often at sub-parts ber billion, or even lower). To acquire sufficient quantities of polycyclic aromatic hydrocarbons with 10 ng/L concentration for CSHIA, more than 1000 L of water must be extracted. Conventional liquid/liquid or solid-phase extraction is not suitable for such large volume extractions. We have developed a new approach that is capable of efficiently sampling sub-parts per billion level waterborne petroleum hydrocarbons for CSIA. We use semipermeable membrane devices (SPMDs) to accumulate hydrophobic contaminants from polluted waters and then recover the compounds in the laboratory for CSIA. In this study, we demonstrate, under a variety of experimental conditions (different concentrations, temperatures, and turbulence levels), that SPMD-associated processes do not induce C and H isotopic fractionations. The applicability of SPMD-CSIA technology to natural systems is further demonstrated by determining the delta13C and deltaD values of petroleum hydrocarbons present in the Pawtuxet River, RI. Our results show that the combined SPMD-CSIA is an effective tool to investigate the source and fate of hydrophobic contaminants in the aquatic environments.

Hazard assessment of a simulated oil spill on intertidal areas of the St. Lawrence River with SPMD-TOX.

Phytoremediation in a simulated crude oil spill was studied with a "minimalistic" approach. The SPMD-TOX paradigm-a miniature passive sorptive device to collect and concentrate chemicals and microscale tests to detect toxicity-was used to monitor over time the bioavailability and potential toxicity of an oil spill. A simulated crude oil spill was initiated on an intertidal freshwater grass-wetland along the St. Lawrence River southwest of Quebec City, Quebec, Canada. Several phytoremediation treatments were investigated; to dissipate and ameliorate the spill, treatments included nutrient amendments with inorganic nitrogen sources (ammonium nitrate and sodium nitrate) and phosphate (super triple phosphate) with and without cut plants, with natural attenuation (no phytoremedial treatment) as a control. Sequestered oil residues were bioavailable in all oil-treated plots in Weeks 1 and 2. Interestingly, the samples were colored and fluoresced under ultraviolet light. In addition, microscale tests showed that sequestered residues were acutely toxic and genotoxic, as well as that they induced hepatic P(450) enzymes. Analysis of these data suggested that polycyclic aromatic hydrocarbons were among the bioavailable residues sequestered. In addition, these findings suggested that the toxic bioavailable fractions of the oil spill and degradation products dissipated rapidly over time because after the second week the water column contained no oil or detectable degradation products in this riverine intertidal wetland. SPMD-TOX revealed no evidence of bioavailable oil products in Weeks 4, 6, 8, and 12. All phytoremediation efforts appeared to be ineffective in changing either the dissipation rate or the ability to ameliorate the oil toxicity. SPMD-TOX analysis of the water columns from these riverine experimental plots profiled the occurrence, dissipation, and influence of phytoremediation on the bioavailability and toxicity of oil products (parent or degradation products).

Overview and comparison of lipid-containing semipermeable membrane devices and oysters (Crassostrea gigas) for assessing organic chemical exposure.

We performed 20-d, flow-through exposures of lipid-containing semipermeable membrane devices (SPMDs) and Pacific oysters (Crassostrea gigas) to three concentrations (nominally 10, 100, and 250 ng/L) of a diverse mixture of polycyclic aromatic hydrocarbons (PAHs). Exposure water was seawater free of particulates larger than 0.1 microm. The results of these controlled laboratory studies demonstrated that SPMDs and oysters concentrate the same chemicals but that the relative amounts accumulated are different. For oysters, the 20-d mean (across treatments) concentration factors (CFs) of test compounds with log Kow < or = 4.8 were much lower (4.0- to 20-fold lower) than those of the same compounds in SPMDs. In contrast, the 20-d CFs of PAHs with log Kow > or = 5.6 in oysters from the low-level treatment were higher than the corresponding CFs for SPMDs. The CFs of these compounds in oysters from the low-level treatment ranged from approximately 3.0- to 13-fold higher than those in oysters from the high-level treatment. This physiologically mediated difference in oyster CFs appears to be linked to active feeding in the low-level treatment and to apparent toxicity-induced cessation of feeding (i.e., valve closure) in the high-level treatment. Because CFs for these compounds in oysters were not independent of exposure concentrations, it follows that tissue levels were not proportional to exposure concentration. However, both sampling approaches have advantages and disadvantages, and the appropriateness of their use depends on the goals of a given study.

Development of a passive, in situ, integrative sampler for hydrophilic organic contaminants in aquatic environments.

Increasingly it is being realized that a holistic hazard assessment of complex environmental contaminant mixtures requires data on the concentrations of hydrophilic organic contaminants including new generation pesticides, pharmaceuticals, personal care products, and many chemicals associated with household, industrial, and agricultural wastes. To address this issue, we developed a passive in situ sampling device (the polar organic chemical integrative sampler [POCIS]) that integratively concentrates trace levels of complex mixtures of hydrophilic environmental contaminants, enables the determination of their time-weighted average water concentrations, and provides a method of estimating the potential exposure of aquatic organisms to the complex mixture of waterborne contaminants. Using a prototype sampler, linear uptake of selected herbicides and pharmaceuticals with log K(ow)s < 4.0 was observed for up to 56 d. Estimation of the ambient water concentrations of chemicals of interest is achieved by using appropriate uptake models and determination of POCIS sampling rates for appropriate exposure conditions. Use of POCIS in field validation studies targeting the herbicide diuron in the United Kingdom resulted in the detection of the chemical at estimated concentrations of 190 to 600 ng/L. These values are in agreement with reported levels found in traditional grab samples taken concurrently.

Uptake and depuration of nonionic organic contaminants from sediment by the oligochaete, Lumbriculus variegatus.

Uptake of sediment-associated contaminants by the oligochaete Lumbriculus variegatus was evaluated after 1, 3, 7, 14, 28, and 56 d of exposure to a field-collected sediment contaminated with DDT and its metabolites, dichlorodiphenyldichloroethane (DDD) and dichlorodiphenyldichloroethylene (DDE), or to a field-collected sediment contaminated with polycyclic aromatic hydrocarbons (PAHs). Depuration of contaminants by oligochaetes in a control sediment or in water was also evaluated over a 7-d period after 28 d of exposure to the field-collected sediments. Accumulation of PAHs with a log octanol-water partitioning coefficient (log Kow) <5.6 typically reached a peak at day 3, followed by a lower plateau between days 7 and 56 of the sediment exposure. Similarly, 4,4'-DDT exhibited a peak in accumulation at day 14 followed by a decline at days 28 and 56. In contrast, accumulation of PAHs with a log Kow >5.6 or DDD and DDE typically exhibited a steady increase from day 1 to about day 14 or 28, followed by a plateau. Therefore, exposures conducted for a minimum of 14 to 28 d better reflected steady-state concentrations for DDT and its metabolites and for PAHs. Depuration rates for DDT and its metabolites and high-Kow PAHs were much higher in organisms held in clean sediment relative to both water-only depuration and model predictions. This suggests that depuration in clean sediment may artificially accelerate depuration of hydrophobic compounds. Comparisons between laboratory-exposed L. variegatus and oligochaetes collected in the field from these sediments indicate that results of laboratory tests can be extrapolated to the field with a reasonable degree of certainty.

HPLC-PFD determination of priority pollutant PAHs in water, sediment, and semipermeable membrane devices.

High performance liquid chromatography coupled with programmable fluorescence detection was employed for the determination of 15 priority pollutant polycyclic aromatic hydrocarbons (PPPAHs) in water, sediment, and semipermeable membrane devices (SPMDs). Chromatographic separation using this analytical method facilitates selectivity, sensitivity (ppt levels), and can serve as a non-destructive technique for subsequent analysis by other chromatographic and spectroscopic techniques. Extraction and sample cleanup procedures were also developed for water, sediment, and SPMDs using various chromatographic and wet chemical methods. The focus of this publication is to examine the enrichment techniques and the analytical methodologies used in the isolation, characterization, and quantitation of 15 PPPAHs in different sample matrices.

Sequestration of priority pollutant PAHs from sediment pore water employing semipermeable membrane devices.

Semipermeable membrane devices (SPMDs) were employed to sample sediment pore water in static exposure studies under controlled laboratory conditions using (control pond and formulated) sediments fortified with 15 priority pollutant polycyclic aromatic hydrocarbons (PPPAHs). The sediment fortification level of 750 ng/g was selected on the basis of what might be detected in a sediment sample from a contaminated area. The sampling interval consisted of 0, 4, 7, 14, and 28 days for each study. The analytical methodologies, as well as the extraction and sample cleanup procedures used in the isolation, characterization, and quantitation of 15 PPPAHs at different fortification levels in SPMDs, water, and sediment were reported previously (Williamson, M.S. Thesis, University of Missouri-Columbia, USA; Williamson et al., Chemosphere (This issue--PII: S0045-6535(02)00394-6)) and used for this project. Average (mean) extraction recoveries for each PPPAH congener in each matrix are reported and discussed. No procedural blank extracts (controls) were found to contain any PPPAH residues above the method quantitation limit, therefore, no matrix interferences were detected. The focus of this publication is to demonstrate the ability to sequester environmental contaminants, specifically PPPAHs, from sediment pore water using SPMDs and two different types of fortified sediment.

Use of triolein-semipermeable membrane devices to assess the bioconcentration and sediment sorption of hydrophobic organic contaminants in the Huaihe River, China.

Triolein-containing semipermeable membrane devices (triolein-SPMD) were deployed I m above the sediments at two sampling sites in the Huaihe River, China, for a period of 28 d. Sediment and fish samples were simultaneously collected from the same sampling sites. Concentrations of substituted benzenes, selected pesticides, polycyclic aromatic hydrocarbon (PAH), and polychlorinated biphenyls (PCBs) were measured in triolein-SPMDs, sediments, and fishes. The concentrations of these hydrophobic organic contaminants (HOCs) in fish and in sediment organic carbon were correlated with HOCs accumulation in triolein-SPMDs. Our results showed reasonably good correlations between the log concentrations of contaminants in fish lipid and in triolein-SPMDs. Good correlations were also found between the log concentrations of contaminants in sediment organic carbon and in triolein-SPMDs (except for PAHs). The results were discussed in terms of the partitioning of hydrophobic organic contaminants among different compartments in the aquatic environment and the suitability of using triolein-SPMDs to predict bioconcentration factor (BCF) and sediment-water partitioning coefficient (K(oc)).

Review of the background and application of triolein-containing semipermeable membrane devices in aquatic environmental study.

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.

Development of the permeability/performance reference compound approach for in situ calibration of semipermeable membrane devices.

Permeability/performance reference compounds (PRCs) are analytically noninterfering organic compounds with moderate to high fugacity from semipermeable membrane devices (SPMDs) that are added to the lipid prior to membrane enclosure. Assuming that isotropic exchange kinetics (IEK) apply and that SPMD-water partition coefficients are known, measurement of PRC dissipation rate constants during SPMD field exposures and laboratory calibration studies permits the calculation of an exposure adjustment factor (EAF). In theory, PRC-derived EAF ratios reflect changes in SPMD sampling rates (relative to laboratory data) due to differences in exposure temperature, membrane biofouling, and flow velocity-turbulence at the membrane surface. Thus, the PRC approach should allow for more accurate estimates of target solute/vapor concentrations in an exposure medium. Undersome exposure conditions, the impact of environmental variables on SPMD sampling rates may approach an order of magnitude. The results of this study suggest that most of the effects of temperature, facial velocity-turbulence, and biofouling on the uptake rates of analytes with a wide range of hydrophobicities can be deduced from PRCs with a much narrower range of hydrophobicities. Finally, our findings indicate that the use of PRCs permits prediction of in situ SPMD sampling rates within 2-fold of directly measured values.