Estrogenicity of pyrethroid insecticide metabolites

There is concern that insecticides are able to mimic the action of 17beta-estradiol by interaction with the human estrogen receptor. Pyrethroids are commonly used insecticides and several have been assessed for potential endocrine disrupting activity by various methods. It has been noted that some metabolites of pyrethroids, in particular, permethrin and cypermethrin, have chemical structures that are more likely to interact with the cellular estrogen receptor than the parent pyrethroid. For this study permethrin and cypermethrin metabolites 3-(4-hydroxy-3-phenoxy)benzyl alcohol, 3-(4-hydroxy-3-phenoxy)benzoic acid, and N-3-(phenoxybenzoyl)glycine were synthesised, and together with the commercially available 3-phenoxybenzyl alcohol, 3-phenoxybenzaldehyde, and 3-phenoxybenzoic acid, were studied in a recombinant yeast assay expressing human estrogen receptors (YES). Three metabolites, 3-phenoxybenzyl alcohol, 3-(4-hydroxy-3-phenoxy)benzyl alcohol, and 3-phenoxybenzaldehyde, showed estrogenic activity of approximately 10(5) less than that of 17beta-estradiol. No activity was observed in the yeast assay for 3-phenoxybenzoic acid, 3-(4-hydroxy-3-phenoxy)benzoic acid, and N-3-(phenoxybenzoyl)glycine. The results from this study show that pyrethroid metabolites are capable of interacting with the human estrogen receptor, and so might present a risk to human health and environmental well being. The impact would be expected to be small, but still add to the overall environmental xenoestrogen load.     

Potentially toxic elements in urban soils: source apportionment and contamination assessment

Soils play a vital role in the quality of the urban environment and the health of its residents. City soils and street dusts accumulate various contaminants and particularly potentially toxic elements (PTEs) from a variety of human activities. This study investigates the current condition of elemental concentration in the urban soils of Hamedan, the largest and the fastest-growing city in western Iran. Thirty-four composite soil samples were collected from 0 to 10 cm topsoil of various land uses in Hamedan city and were analyzed for total concentration of 63 elements by ICP-MS. The possible sources of elemental loadings were verified using multivariate statistical methods (principal component analysis and cluster analysis) and geochemical indices. The spatial variability of the main PTEs was mapped using geographic information system (GIS) technique. The results revealed a concentration for As, Co, Cr, Mn, Mo, Ni, and V in the soil samples comparable to the background values as well as a range of associations among these elements in a single component suggesting geogenic sources related to geological and pedogenic processes, while the soils mostly presented a moderate to considerable enrichment/contamination of Cd, Zn, Pb, and Sb and moderate enrichment/contamination of Cu, Zn, and Mo. It was found that anthropogenic factors, vehicular traffic in particular, control the concentration of a spectrum of elements that are typical of human activities, i.e., Cd, Cu, Hg, Pb, Sb, and Zn. Lead and Sb were both the most enriched elements in soils with no correlation with land use highlighting general urban emissions over time and the impact of transport networks directly on soil quality. The highest concentrations of As were recorded in the southern part of the city reflecting the influence of metamorphic rocks. The effect of the geological substrate on the Co and Ni contents was confirmed by their maximum concentrations in the city’s marginal areas. However, high spatial variability of urban elements’ contents displayed the contribution of various human activities. In particular, the increased concentration of Cd, Sb, and Pb was found to be consistent with the areas where vehicular traffic is heaviest.     

An FTIR investigation of isocyanate skin absorption using in vitro guinea pig skin

Isocyanates may cause contact dermatitis, sensitization and asthma. Dermal exposure to aliphatic and aromatic isocyanates can occur in various exposure settings. The fate of isocyanates on skin is an important unanswered question. Do they react and bind to the outer layer of skin or do they penetrate through the epidermis as unreacted compounds? Knowing the kinetics of these processes is important in developing dermal exposure sampling or decontamination strategies, as well as understanding potential health implications such exposure may have. In this paper the residence time of model isocyanates on hairless guinea pig skin was investigated in vitro using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrometry. Model isocyanates tested were octyl isocyanate, polymeric hexamethylene diisocyanate isocyanurate (pHDI), polymeric isophorone diisocyanate isocyanurate (pIPDI) and methylenediphenyl diisocyanate (MDI). Isocyanates in ethyl acetate (30 microL) were spiked directly on the skin to give 0.2-1.8 micromol NCO cm(-2) (NCO = -N=C=O), and absorbance of the isocyanate group and other chemical groups of the molecule were monitored over time. The ATR-FTIR findings showed that polymeric isocyanates pHDI and pIPDI may remain on the skin as unreacted species for many hours, with only 15-20% of the total isocyanate group disappearing in one hour, while smaller compounds octyl isocyanate and MDI rapidly disappear from the skin surface (80+% in 30 min). Isocyanates most likely leave the skin surface by diffusion predominantly, with minimal reaction with surface proteins. The significance of these findings and their implications for dermal exposure sampling and isocyanate skin decontamination are discussed.     

Determination of relative assay response factors for toxic chlorinated and brominated dioxins/furans using an enzyme immunoassay (EIA) and a chemically-activated luciferase gene expression cell bioassay (CALUX)

Determination of toxic activity requires knowledge of both the concentration and toxicity to evaluate the risk for adverse human health and environmental effects. A chemically-activated luciferase gene expression cell bioassay system (CALUX) and an antibody-based method enzyme immunoassay (EIA) were used to detect the dioxin-like response of several polybrominated, polychlorinated, and polybrominated/chlorinated dibenzo-p-dioxins/furans (PBDDs/Fs, PCDDs/Fs, and PBCDDs/Fs, respectively). It has been suggested that the biological activity of the brominated and mixed bromo/chloro compounds is similar to their chlorinated analogues (measured by binding to the Ah receptor). PBDD/F, PCDD/F, and PBCDD/F laboratory standards exhibited biological activity ranging over three orders of magnitude. The highest relative potency (REP) values from CALUX analysis, when compared to 2,3,7,8-TCDD, were 2,3,7,8-TBDD at 0.99 (± 0.07), 1,2,3,7,8-PeCDD at 0.69, and 2-Br-3,7,8-TriCDD at 0.72 (± 0.02). Cross-reactivities were calculated using EIA for several PBDDs/Fs and PBCDDs. The highest percent cross-reactivity was found for 2,3,7,8-TBDD at 138 (± 34%), and 2,3,7-TriBDD at 84 (± 36%).     

Leaching of zinc from tire wear particles under simulated estuarine conditions

Tire wear particles (TWP) abraded from end-of-life passenger car tires have been added at a concentration of 1 g L⁻¹ to river water, sea water and mixtures thereof in order to examine the chemical controls on the leaching of Zn from the rubber matrix. Results of time-dependent experiments conducted over a period of 5 days were consistent with a diffusion controlled leaching mechanism with rate constants of about 0.04 mg L⁻¹ h^−1/2 in river water and between about 0.02 and 0.03 mg L⁻¹ h^−1/2 in sea water. Additional experiments revealed a reduction in Zn dissolution with both increasing salinity and pH and enhancement of leaching in the presence of fluorescent light compared with dark conditions. In corresponding experiments conducted in the presence of a fixed quantity (0.8 g L⁻¹) of clean, fractionated estuarine sediment, aqueous Zn concentrations were reduced by at least an order of magnitude. Increasing the quantity of sediment resulted in a progressive reduction in Zn concentration until an apparent equilibrium was achieved, with partition coefficients defining the sediment-water distribution of Zn of about 550 mL g⁻¹ and 270 mL g⁻¹ in river water and sea water, respectively. Results are interpreted in terms of the dissolution of ZnO and other residual complexes from the matrix and the subsequent, rapid adsorption of Zn²⁺ ions to coexistent estuarine sediment. The findings of the study are discussed in terms of their implications for the transport, fate and effects of TWP Zn in aquatic environments that are likely to receive urban runoff.     

Sourcing sediment using multiple tracers in the catchment of Lake Argyle,Northwestern Australia

Control of sedimentation in large reservoirs requires soil conservation at the catchment scale. In large, heterogeneous catchments, soil conservation planning needs to be based on sound information, and set within the framework of a sediment budget to ensure that all of the potentially significant sources and sinks are considered. The major sources of sediment reaching the reservoir, Lake Argyle, in tropical northwestern Australia, have been determined by combining measured sediment fluxes in rivers with spatial tracer-based estimates of proportional contributions from tributaries of the main stream entering the lake, the Ord River. The spatial tracers used are mineral particle magnetics, the strontium isotopic ratio, and the neodymium isotopic ratio. Fallout of ¹³⁷Cs has been used to estimate the proportion of the sediment in Lake Argyle eroded from surface soils by sheet and rill erosion, and, by difference, the proportion eroded from subsurface soils by gully and channel erosion. About 96% of the sediment in the reservoir has come from less than 10% of the catchment, in the area of highly erodible soils formed on Cambrian-age sedimentary rocks. About 80% of the sediment in the reservoir has come from gully and channel erosion. A major catchment revegetation program, designed to slow sedimentation in the reservoir, appears to have had little effect because it did not target gullies, the major source of sediment. Had knowledge of the sediment budget been available before the revegetation program was designed, an entirely different approach would have been taken.     

The release of phosphorus to porewater and surface water from river riparian sediments

Sediments can be both a source and a sink of dissolved phosphorus (P) in surface water and shallow groundwater. Using laboratory mesocosms, we studied the influence of flooding with deionized water and simulated river water on P release to solution using sediment columns taken from a riparian wetland. The mesocosm incubation results showed that rather than retaining nutrients, sediments in the riparian zone may be a significant source of P. Concentrations of dissolved P in porewater reached more than 3 mg L(-1) and in surface water over 0.8 mg L(-1) within a month of sediment inundation. The reductive dissolution of P-bearing iron (Fe) oxides was the likely mechanism responsible for P release. Dissolved P to Fe molar ratios in anaerobic samples were approximately 0.45 when columns were flooded with water that simulated the chemistry of the adjacent river. This suggests there was insufficient Fe in the anaerobic samples to precipitate all P if the solutions were oxygenated or transported to an aerobic environment. If the anaerobic wetland solutions were delivered to oxygenated rivers and streams adjacent to the riparian zone, the equilibrium concentration of P in these systems could rise. The timing of P release was inversely related to the nitrate (NO3-) concentration in floodwater. This indicates that in riparian zones receiving low nitrate loads, or where NO3- loads are being progressively reduced, the risk of dissolved P release may increase. These findings present particular challenges for restoration and management in riparian areas.     

Effects of sewage effluent discharge on the abundance, condition and mortality of hulafish, Trachinops taeniatus (Plesiopidae)

The effects of sewage effluent on the abundance, condition (length and reproduction) and mortality of hulafish Trachinops taeniatus were investigated at multiple outfall and control locations on the central coast of New South Wales, Australia. Underwater visual surveys found consistently fewer T. taeniatus at locations where sewage was discharged compared to control locations. The condition of T. taeniatus was investigated by comparing mean length and reproductive indices of fish from two outfall and two control locations. Fish from the largest outfall location were significantly smaller in comparison with fish from control locations. Gravid female fish from outfall locations had similar gonadosomatic indices but a significantly greater number of eggs and smaller size of eggs in comparison with fish from control locations. Mortality of T. taeniatus was investigated during 2-week, in situ, caging experiments at multiple locations and times and 80% of fish survived, although mortalities of up to 73% per cage were recorded at one sewage outfall. T. taeniatus may be a suitable environmental indicator species of sewage pollution.     

Response of a solid-liquid two-phase partitioning bioreactor to transient BTEX loadings

A two-phase partitioning bioreactor (TPPB) consisting of an aqueous phase containing a bacterial consortium and a polymeric phase of silicone rubber pellets (solid volume fraction 0.1) was used to treat a gaseous waste stream containing benzene, toluene, ethylbenzene and o-xylene (BTEX). The function of the solid polymer phase was to absorb/desorb the gaseous volatile organic compounds providing a buffering effect to protect the cells from high transient loadings and to sequester the BTEX for subsequent degradation. The TPPB was subjected to high and fluctuating inlet loadings of BTEX in the form of 4h step changes of 2, 4, 6 and 10 times the nominal inlet loading of 60 gm(-3) h(-1) total BTEX in approximately equal amounts, and removal efficiencies and elimination capacities were determined. It was found that overall removal efficiencies of greater than 95% can be achieved while obtaining overall elimination capacities of up to 282 gm(-3) h(-1) during transient operation and TPPB operation succumbs to toxic substrate levels between step changes of 6 and 10 times the nominal loading value (360-600 gm(-3) h(-1)). BTEX concentrations in the aqueous phase and the polymer phase of the TPPB were monitored throughout the imposed step changes to determine the extent to which the sequestering phase can buffer the aqueous phase from BTEX. With the polymer phase comprising only 10% of the total working volume of the reactor, the polymer beads accounted for up to 93%, 91% and 70% of the total BTEX present in the working volume for step changes of 2, 4 and 6 times the nominal loading, respectively.