Runoff and surface-water effluents commonly contain suspended solids. Adsorption to suspended particles and the associated dissolved organic matter (DOM) may significantly decrease the freely dissolved concentration of a hydrophobic compound and, hence, its availability to aquatic organisms. In the present study, we evaluated phase distribution and bioaccumulation of two synthetic pyrethroids, bifenthrin and permethrin, in water samples containing suspended solids from different source sediments. Uptake of [14C]bifenthrin or [14C] permethrin by Daphnia magna after 24 h consistently decreased with increasing levels of suspended solids in the range of 0 to 200 mg/L. The trend of decrease was closely mimicked by pesticide accumulation on polydimethylsiloxane (PDMS) fibers exposed under the same conditions, and the ratio of body residues in D. magna to the concentration detected in the PDMS fiber was consistently around 2.4. Regression analysis showed that the pesticide adsorbed on particles or DOM was completely unavailable to D. magna for uptake during the 24-h exposure. The relative contribution of particles and DOM to the reduced bioavailability depended on the organic matter content and the texture of the source sediment. The influence from particles was predominant for sandy sediments, but contribution from DOM became comparable to or even greater than particles when the organic matter content of the source sediment was 1% or greater. The inhibitory effects of suspended solids on bioavailability should be considered when monitoring runoff and surface-water effluents for synthetic pyrethroids. The proposed PDMS method is simple and inexpensive, and it may serve as an effective option for obtaining ecotoxicologically relevant concentrations.

Pyrethroids are widely used insecticides in both agricultural and urban environments, and their potential movement to surface streams and toxicity to susceptible aquatic species is an emerging concern. Natural surface waters usually contain low levels of dissolved organic matter (DOM). Limited data have shown that DOM preparations can significantly alter the bioavailability and toxicity effects of pyrethroids. However, the importance of these effects in natural waters has not been investigated. In this study we measured uptake and acute toxicity of permethrin and cyfluthrin by Daphnia species in 15 surface water samples. Low levels of DOM (3-20 mg L(-1)) inhibited cyfluthrin uptake by Daphnia magna and acute toxicity to Ceriodaphnia dubia in most samples. For permethrin, the effects of DOM on bioavailability and toxicity were generally not significant. The effects of DOM on bioavailability of cyfluthrin could not be explained from the DOC concentration alone, suggesting that properties of DOM were also important in regulating bioavailability. Regression of K DOC with selected DOM properties revealed significant dependence of K DOC on the carboxylic acid content of DOM. Moreover, concentrations sensed by solid-phase microextraction (SPME) fibers were well correlated with the observed changes in bioaccumulation by D. magna and acute toxicity to C. dubia. Therefore, selective sampling methods such as SPME may be used for measuring the bioavailable concentrations of pyrethroids in waters with naturally occurring DOM levels and predicting the actual toxicity effects.

Microbial degradation is the most important removal process for hydrophobic organic compounds (HOCs) in soil or sediment, and chemical availability is often a governing factor. However, the availability of HOCs in the sorbed forms is still a topic of debate. In this study, we applied rigorous kinetics analysis to the relationship between the freely dissolved concentration (Cfree) of phenanthrene (PHE) measured by polydimethylsiloxane (PDMS) fibers and its degradation by a PAH degrading bacterium PYR-1 under a range of soil conditions. In solutions of soils with varying organic carbon (OC) contents, Cfree of PHE decreased from 28.63 +/- 2.15 to 0.79 +/- 0.04 microg L(-1) when the soil OC content changed from 0.23 to 7.1%. Correlation analysis between Cfree and PHE mineralization rates revealed that the bacterium quickly exhausted the PHE pool available for equilibrium distribution, including Cfree and the reversibly sorbed fraction, after which the sequestered pool was utilized. In addition, unlike changes in Cfree, degradation rates of total PHE only varied by a factor of 1.6-2.1 over the same soil OC range. Regression analysis using a multivariate relationship showed that soil OC content and porosity properties such as soil surface area had a compounded effect on the microbial availability of PHE in these soils. The kinetics analysis using Cfree, as proposed in this study, may be applied to other HOCs to gain a better understanding of microbial availability under various conditions.

Pyrethroid insecticides are widely used in both agricultural and urban environments. Pyrethroids have been frequently detected in California, USA, stream bed sediments. Pyrethroids are strongly hydrophobic so their bioavailability is determined by their sorption to sediment. In the present study, we used disposable polydimethylsiloxane (PDMS) fibers to sample from the freely dissolved (effective) permethrin concentration that governs bioaccumulation and toxicity, and tested the correlation of those measurements with uptake by Chironomus tentans. In sediments that were incrementally diluted with silica sand, both PDMS fiber and organic carbon (OC) normalized sediment concentrations were highly correlated with C. tentans permethrin uptake. However, for multiple sediments with OC ranging from 1.4 to 27%, C. tentans permethrin uptake showed a better correlation with PDMS fiber concentrations than sediment OC-normalized concentrations. We conclude that the qualitative properties of sediment OC influence permethrin phase distribution and therefore the bioavailability of permethrin in sediment-water systems. Consequently selective methods such as PDMS fibers yield improved estimates of bioaccumulation and toxicity as such methods detect freely dissolved permethrin concentrations in the sediment.