Determining the toxicity of organic compounds to the nematode Caenorhabditis elegans based on aqueous concentrations.

Caenorhabditis elegans is used for assessing the toxicity of chemicals in aqueous medium. However, chemicals can absorb to the bacterial food, which reduces the freely dissolved concentrations of the tested compounds. Thus, based on total or nominal concentrations, toxicity is underestimated, resulting in misleading assumptions on toxicity mechanisms or comparisons to other test organisms. As the verification of freely dissolved exposure concentrations (Cfree) is challenging in small test systems, simple partitioning models might by a good option for estimating Cfree. Therefore, C. elegans was exposed to seven differently acting organic chemicals with varying hydrophobicities, thus also different affinities to bind to the food of C. elegans. Measured concentrations of the dissolved aqueous and the bacterial-bound fraction allowed the calculation of binding constants (Kb). Experimental Kb were comparable to literature data of hydrophobic chemicals and correlated well with their hydrophobicity, expressed as log KOW. The chronic toxicity of the various compounds on C. elegans' reproduction, based on their aqueous concentration, was weakly related to their log KOW. Toxicity expressed based on chemical activity and comparisons with a baseline toxicity model, nevertheless, suggested a narcotic mode of action for most hydrophobic compounds (except methylisothiazolinone and trichlorocarbanilide). Although revealing a similar toxicity ranking than Daphnia magna, C. elegans was less sensitive, probably due to its ability to reduce its internal concentrations by means of its very impermeable cuticle or by efficient detoxification mechanisms. It could be shown that measured aqueous concentrations in the nematode test system corresponded well with freely dissolved concentrations that were modeled using simple mass-balance models from nominal concentrations. This offers the possibility to estimate freely dissolved concentrations of chemicals from nominal concentrations, making routine testing of chemicals and their comparison to other species more accurate.

Techniques for monitoring bioavailable organic pollutants in sediment: Application of poly(methyl methacrylate) as a passive sampler.

A poly(methyl methacrylate) (PMMA) passive sampler was applied to harbor sediment to examine whether the substrate could be used as a tool to measure freely dissolved concentrations of contaminants. An ex situ method required at least 1 g of PMMA to detect freely dissolved polycyclic aromatic hydrocarbons (PAHs) in sediment with <100 ng/g dry weight. Two weeks were sufficient to reach equilibrium under 180 rpm for PAHs with a molar volume of <250 cm3/mol. For the in situ method, a deployment time of four months was sufficient to measure PAHs with a molar volume up to 250 cm3/mol in the sediment bed. The PMMA passive sampler could be used to measure the bioavailable fraction of PAHs in porewater, reflecting the complex properties of sediment with strong sorption such as black carbons.

Possibilities of poly(methyl methacrylate) as a passive sampler for determination of bioavailable concentrations in seawater.

Solvent-treated poly(methyl methacrylate) (PMMA) was recently introduced as a passive sampler for determining bioavailable concentrations, i.e., freely dissolved concentrations. However, the much knowledge required to obtain accurate bioavailable concentrations using the thus treated PMMA, applied in a marine environment, is still lacking. In this study, uptake experiments with PMMA after solvent treatment were conducted to investigate its uptake capacity and the effects of water temperature and salinity on the PMMA-water partition coefficient (KPMMA-W) for polycyclic aromatic hydrocarbons (PAHs). Thus, PMMA passive samplers preloaded with performance reference compounds were exposed to seawater to first estimate the deployment time and then to confirm if the PMMA could give the residual concentrations of PAH in mussel. The less hydrophobic PAHs (log octanol-water partition coefficient < 5.5) had higher uptake capacity of PMMA-uptake was increased by a factor of up to 10. Whereas for these PAHs the KPMMA-W values and seawater temperature showed a parabolic relationship, the effect of salinity on KPMMA-W was not observed. The less hydrophobic PAH concentrations in seawater can be measured using the PMMA passive sampler over a period of about three weeks. For the PAHs detected in both PMMA and mussel, the PAH concentrations in mussel predicted from PMMA were found to be within one order of magnitude of the measured concentrations. This, therefore, suggests that solvent-treated PMMA could be used as a passive sampler to provide information on bioavailable concentrations for less hydrophobic PAHs.

Sorption kinetics of parent and substituted PAHs for low-density polyethylene (LDPE): Determining their partition coefficients between LDPE and water (KLDPE) for passive sampling.

Low-density polyethylene (LDPE) has been widely used as a sorbent for passive sampling of hydrophobic organic contaminants (HOCs) in aquatic environments. However, it has seen only limited application in passive sampling for measurement of freely dissolved concentrations of parent and substituted PAHs (SPAHs), which are known to be toxic, mutagenic and carcinogenic. Here, the 16 priority PAHs and some typical PAHs were selected as target compounds and were simultaneously determined by gas chromatography-mass spectrometer (GC-MS). Some batch experiments were conducted in the laboratory to explore the adsorption kinetics of the target compounds in LDPE membranes. The results showed that both PAHs and SPAHs could reach equilibrium status within 19-38 days in sorption kinetic experiments. The coefficients of partitioning between LDPE film (50 µm thickness) and water (KLDPE) for the 16 priority PAHs were in good agreement with previously reported values, and the values of KLDPE for the 9 SPAHs are reported in this study for the first time. Significant linear relationships were observed, i.e., log KLDPE = 0.705 × log KOW + 1.534 for PAHs (R2 = 0.8361, p < 0.001) and log KLDPE = 0.458 × log KOW + 3.092 for SPAHs (R2 = 0.5609, p = 0.0077). The selected LDPE film was also proven to meet the condition of "zero sink" for the selected target compounds. These results could provide basic support for the configuration and in situ application of passive samplers.

Polyoxymethylene passive samplers to assess the effectiveness of biochar by reducing the content of freely dissolved fipronil and ethiprole.

An equilibrium passive sampler based on polyoxymethylene (POM) was used to determine the freely dissolved concentrations (Cfree) of fipronil and ethiprole. The sorption equilibrium times of fipronil and ethiprole in POM were 14.2d and 24.0d, respectively. The POM-water partitioning coefficients (logKPOM-water) were 2.6 for fipronil and 1.4 for ethiprole. The method was further used to evaluate the sorption behavior of biochars which produced by pyrolysis of Magnolia wood (Magnolia denudata) at 300°C, 500°C and 700°C. The amounts of target compounds adsorbed increased with increasing pyrolysis temperature of the biochars. Biochars characterized by a low polarity index had better sorption capacity for the target compounds. The additions of biochars to sediment were effective in reducing Cfree, and the enhancement was found to be more pronounced with high biochar content. Cfree in sediment with more organic matter was significantly higher after biochar addition. Increasing the sediment-biochar contact time from 7 to 30d resulted in an increase in sorption of the compounds. We conclude that Magnolia wood biochar effectively reduces the content of freely dissolved fipronil and ethiprole content in sediment.