The occurrence of chlorpyrifos, diazinon, pyrethroids, and fipronil was investigated in two watersheds along the southern California coast. Paired surface water and sediment samples were collected under dry and wet (after significant rain events) weather conditions. Insecticide concentrations in water and sediment were higher following rain events than during the dry season. Chlorpyrifos was the most frequently detected compound (>88%). Pyrethroids were detected in 74 and 100% of the water and sediment samples, respectively, with bifenthrin detected most frequently. Trans-permethrin was detected at the highest concentration followed by bifenthrin. Bifenthrin and trans-permethrin water concentrations were significantly correlated (P < 0.01) with the suspended solid level, suggesting transport facilitated by suspended particles. In 80% of the wet season samples with 100% of Ceriodaphnia dubia mortality, chlorpyrifos concentrations were >100 ng L(-1). Sediment pyrethroid levels (0.5-1100 ng g(-1)) were frequently higher than the respective Hyalella azteca LC(50) values, with bifenthrin as the primary contributor of H. azteca toxicity.

No abstract

No abstract

No abstract

Polybrominated diphenyl ethers (PBDEs) are a class of widely used brominated flame retardants with strong hydrophobicity. Due to their strong affinity for organic matter, accurate measurement of adsorption coefficients for PBDEs using conventional batch methods can be confounded by biases caused by their sorption to dissolved organic carbon (DOC). In this study, sorption isotherms were constructed for BDE-47 and BDE-99 in sediments by using different methods to measure the aqueous phase concentration Cw. Upon centrifugation, Cw measured by automated solid-phase microextraction (Cw-SPME) was consistently smaller than by liquid-liquid extraction (Cw-LLE), suggesting substantial association of PBDEs with DOC. Significant underestimations (1.2-106-fold) of sediment-water partition coefficient Kd occurred when Cw was measured by LLE. The log KDOC values derived from the SPME measurements ranged from 5.10 to 8.02 for eight congeners from BDE-28 to BDE-183, suggesting a strong tendency for PBDEs to complex with DOC. This study showed that PBDE congeners have larger sorption coefficients than would be measured by the conventional method. The high affinity to DOC also means a potential for DOC-facilitated transport, thus enhancing the environmental mobility of PBDEs.

No abstract

Despite their strong hydrophobicity, recent studies showed widespread occurrence of pyrethroid in downstream surface waters bodies. In this work, the effect of dissolved organic carbon (DOC) on the sorption and desorption of pyrethroids in sediment was evaluated to understand the role of DOC in facilitating pyrethroid transport. Presence of DOC from three sources at 38 ± 2 mg L⁻¹ in the aqueous phase decreased pesticide sorption to a sediment by 1.7 to 38.9 times and increased their desorption by 1.2 to 41.4 times. The effect on pyrethroid sorption to the sediment was linear. In addition, interactions between DOC and pyrethroids, when taking place prior to the contact with sediment, decreased sorption of some pyrethroids even further, implying that DOC-pyrethroid complexs were relatively stable in solution. DOC sources with higher contents of carboxylic and phenolic groups were found to have a higher potential to associate with pyrethroids. The DOC-water partition coefficients (K(DOC)) obtained by solid-phase microextraction measurement were significantly correlated (P < 0.01) with K(d) values measured for the sediment. These results provide evidence that DOC increases the distribution of pyrethroids from the sediment to the solution phase and plays an important role in mobilizing pyrethroids in runoff and surface streams.

No abstract