Vapour pressures, aqueous solubilities, Henry's Law constants, and octanol/water partition coefficients of a series of mixed halogenated dimethyl bipyrroles

Basic physical-chemical properties of five bromine and chlorine containing mixed halogenated dimethyl bipyrroles (HDBPs) were determined using established methods. Subcooled liquid vapour pressures (P(o)(L,25)), aqueous solubilities (S(w,25)), and octanol/water partition coefficients (K(ow)) were determined using the gas chromatography-retention time, generator column, and slow-stirring methods, respectively. Henry's Law constants (H25) were estimated using experimentally-derived P(o)(L) and S(w,25) data. Values of all four properties were generally similar to those reported for other polyhalogenated aromatic compounds [P(o)(L,25) = (7.55-191) x 10(-6) Pa; S(w,25) = (1.0-1.9) x 10(-5) g/l; log K(ow) = 6.4-6.7; H25 = 0.0020-0.14 Pa m3/mol]. The effect of replacing a chlorine with a bromine atom significantly decreased P(o)(L,25) (log P(o)(L,25) = -0.4197 (# bromine atoms) - 2.643, p<0.01) and H25 (log H25 = -0.508 (# bromine atoms) + 0.394, p<0.02). There were no significant effects of bromine/chlorine substitution on S(w,25) or K(ow). A simple Level I equilibrium partitioning model predicted the environmental behaviour of HDBPs to be similar to a tetrabrominated diphenyl ether. Only slight differences in behaviour amongst HDBP congeners were predicted since substitution of a bromine for a chlorine (Cl/Br substitution) atom had less effect than H/Cl or H/Br substitution on P(o)(L,25), S(w,25), H25, and K(ow).     

An assessment of the emissions inventory processing systems EMS-2001 and SMOKE in grid-based air quality models

In the United States, emission processing models such as Emissions Modeling System-2001 (EMS-2001), Emissions Preprocessor System-Version 2.5 (EPS2.5), and the Sparse Matrix Operator Kernel Emissions (SMOKE) model are currently being used to generate gridded, hourly, speciated emission inputs for urban and regional-scale photochemical models from aggregated pollutant inventories. In this study, two models, EMS-2001 and SMOKE, were applied with their default internal data sets to process a common inventory database for a high ozone (O3) episode over the eastern United States using the Carbon Bond IV (CB4) chemical speciation mechanism. A comparison of the emissions processed by these systems shows differences in all three of the major processing steps performed by the two models (i.e., in temporal allocation, spatial allocation, and chemical speciation). Results from a simulation with a photochemical model using these two sets of emissions indicate differences on the order of +/- 20 ppb in the predicted 1-hr daily maximum O3 concentrations. It is therefore critical to develop and implement more common and synchronized temporal, spatial, and speciation cross-reference systems such that the processes within each emissions model converge toward reasonably similar results. This would also help to increase confidence in the validity of photochemical grid model results by reducing one aspect of modeling uncertainty.     

The OECD Validation Program of the H295R Steroidogenesis Assay for the Identification of In Vitro Inhibitors and Inducers of Testosterone and Estradiol Production. Phase 2: Inter-Laboratory Pre-Validation Studies (8 pp)

Background, Goals and Scope In response to concerns that have been raised about chemical substances that may alter the function of endocrine systems and result in adverse effects on human health, an OECD initiative was undertaken to develop and validate in vitro and in vivo assays to identify chemicals that may interfere with endocrine systems of vertebrates. Here we report on studies that were conducted to develop and standardize a cell-based screening assay using the H295R cell line to prioritize chemicals that may act on steroidogenic processes in humans and wildlife. These studies are currently ongoing as part of the ‘Special Activity on the Testing and Assessment of Endocrine Disruptors’ within the OECD Test Guidelines Program to review, develop, standardize, and validate a number of in vitro and in vivo toxicological assays for testing and assessment of chemicals concerning their potential to interact with the endocrine system of vertebrates. Study Design Six laboratories from five countries participated in the pre-validation studies. Each laboratory tested the effects of three model chemicals on the production of testosterone (T) and estradiol (E2) using the H295R Steroidogenesis Assay. Chemicals tested were well described inducers or inhibitors of steroidogenic pathways (forskolin, prochloraz and fadrozole). All experiments were conducted in 24 well plates following standard protocols. Six different doses per compound were analyzed in triplicate per plate. A quality control (QC) plate was run in conjunction with the chemical exposure plate to account for inter-assay variation. Each chemical exposure was conducted two or three times. Results All laboratories successfully detected increases and/or decreases in hormone production by H295R cells after exposure to the different model compounds and there was good agreement in the pattern of response for all groups. Forskolin increased both T and E2 while fadrozole and prochloraz decreased production of both hormones. All chemicals affected hormone production in a dose-dependent manner with the exception of fadrozole which caused maximum inhibition of E2 at the two least concentrations tested. Some inter-laboratory differences were noted in the alteration of hormone production measured in chemically exposed cells. However, with the exception of the production of T measured at one laboratory in cells exposed to forskolin, the EC₅₀s calculated were comparable (coefficients of variation 34–49%) for all hormones. Discussion and Perspectives The results indicated that the H295R Steroidogenesis Assay protocol was robust, transferable and reproducible among all laboratories. However, in several instances that were primarily related to one laboratory there were unexplained minor uncertainties related to the inter-laboratory hormone production variation. Based on the findings from this Phase 2 prevalidation study, the H295R Steroidogenesis Assay protocol is currently being refined. The next phase of the OECD validation program will test the refined protocol among the same group of laboratories using an extended set of chemicals (∼30) that will include positive and negative chemical controls as well as a broad spectrum of different potential inducers and inhibitors of steroidogenic pathways. Submission Editor: Dr. Carsten Brühl (bruehl@uni-landau.de)     

Metal behaviour in an estuary polluted by acid mine drainage: the role of particulate matter

The concentrations of dissolved and suspended particulate Cd, Cu and Zn have been determined in water samples obtained during two axial transects of the Rio Tinto-Huelva Ria system in south-west Spain, which is severely impacted by acid mine drainage. Although the metal concentrations in both phases were elevated, dissolved metals were dominant and, in the upper estuary, constituted > 99% of total metal in the water column. Dissolved metals behaved non-conservatively on each transect, with maximum concentrations in the low salinity region. There was no evidence of metal adsorption within the turbidity maximum zone, despite the high specific surface areas of resuspending particles. Measurements of electrophoretic mobility showed that the suspended particulate matter (SPM) had a positive surface charge in the salinity range 0-4, where the waters had a pH < 3. Desorption experiments were carried out in which SPM from the turbidity maximum zone was resuspended in coastal seawater. The desorption of the metals was monitored for 24 h, using anodic stripping voltammetry (ASV) to detect the variation in total dissolved Cd, Cu and Zn and the species of Cu and Zn. Total dissolved Cd concentrations doubled during the incubation period, whereas the concentration of total dissolved Cu declined and that of Zn remained rather constant. The ASV-labile fraction of dissolved Cu and Zn showed an initial sharp release followed by a slower uptake. However, desorption was shown to be a minor source of dissolved metals and made little contribution to the non-conservative behaviour in the low salinity zone. The results are used to predict the effects of acid mine drainage on estuarine ecology.     

Porous organoclay composite for the sorption of polycyclic aromatic hydrocarbons and pentachlorophenol from groundwater

Complex mixtures of hazardous chemicals such as polycyclic aromatic hydrocarbons (PAHs) in contaminated soil and groundwater can have severe and long-lasting effects on health. The evidence that these contaminants can cause adverse health effects in animals and humans is rapidly expanding. The frequent and wide-spread occurrence of PAHs in groundwater makes appropriate intervention strategies for their remediation highly desirable. The core objective of this research was to assess the ability of a clay-based composite to sorb and remove toxic contaminants from groundwater at a wood-preserving chemical waste site. Treatment efficiencies were evaluated using either effluent from an oil-water separator (OWS) or a bioreactor (B2). The effluent water from these units was passed through fixed bed columns containing either an organoclay composite or granular activated carbon. The sorbent columns were placed in-line using existing sampling ports at the effluent of the OWS or B2. Individual one-liter samples of treated and untreated effluent were collected in Kimax bottles over the course of 78 h (total of 50 samples). Subsequently each sample was extracted by solid phase extraction methodology, and pentachlorophenol (PCP) and PAH concentrations were quantitated via GC/MS. Columns containing porous organoclay composite, i.e. sand-immobilized cetylpyridinium-exchanged low-pH montmorillonite clay (CP/LPHM), were shown to reduce the contaminant load from the OWS effluent stream by 97%. The concentrations of benzo[a]pyrene (BaP) and PCP were considerably reduced (i.e. >99%). An effluent stream from the bioreactor was also filtered through columns packed with composite or an equivalent amount of GAC. Although the composite reduced the majority of contaminants (including BaP and PCP), it was less effective in diminishing the levels of lower ring versus higher ring PAHs. Conversely, GAC was more effective in removing the lower ring PAHs, except for naphthalene and PCP. The effectiveness of sorption of PCP from the OWS effluent by the composite was confirmed using a PCP-sensitive adult hydra bioassay previously described in our laboratory. The findings of this initial study have delineated differences between CP/LPHM and GAC for groundwater remediation, and suggest that GAC (instead of sand) as the solid support for organoclay may be more effective for the treatment of contaminated groundwater under field conditions than GAC or CP/LPHM alone. Further work is ongoing to confirm this conclusion.     

Environmental impact of two successive chemical treatments in a small shallow eutrophied lake: Part II. Case of copper sulfate

The appearance of cyanobacteria ( > 10 colony per ml) was not prevented after alum treatment. In order to prevent cyanobacteria efflorescences in a small shallow polymictic lake (Courtille, France), copper sulfate was applied. Treatment level was 63 microg 1(-1) as Cu2+ from CUSO4, 5 H2O. Cyanobacteria were kept under control during the summer. Microcystis sp. completely disappeared, which allowed swimming in the lake throughout the tourist season. Microcystis only reappeared 2 months after the treatment. Copper content in the water column only returned to its background level 2 months after copper addition. This high residence time of copper in the water might have been caused by complexation and adsorption of copper on natural organic matter, whose level was high in the ecosystem studied. A mechanism of transfer of 'truly' dissolved copper towards particulate copper has been underlined and explains the disappearance of this fraction of copper in the water column.     

Optimal patch time allocation for time-limited foragers

The Charnov Marginal Value Theorem (MVT) predicts the optimal foraging duration of animals exploiting patches of resources. The predictions of this model have been verified for various animal species. However, the model is based on several assumptions that are likely too simplistic. One of these assumptions is that animals are living forever (i.e., infinite horizon). Using a simple dynamic programming model, we tested the importance of this assumption by analysing the optimal strategy for time-limited foragers. We found that, for time-limited foragers, optimal patch residence times should be greater than those predicted from the classic, static MVT, and the deviation should increase when foragers are approaching the end of their life. These predictions were verified for females of the parasitoid Anaphes victus (Hymenoptera: Mymaridae) exploiting egg patches of its host, the carrot weevil Listronotus oregonensis (Coleoptera: Curculionidae). As predicted by the model, females indeed remained for a longer time on host patches when they approached the end of their life. Experimental results were finally analysed with a Cox regression model to identify the patch-leaving decision rules females used to behave according to the model’s predictions.     

The Residence Time of Settling Particles in the Surface Mixed Layer

The transport from the upper mixed layer into the pycnocline of particles with negative buoyancy is considered. Assuming the hydrodynamic parameters to be time- independent, an adjoint model is resorted to that provides a general expression of the residence time in the mixed layer of the constituent under study. It is seen that the residence time decreases as the settling velocity increases or the diffusivity decreases. Furthermore, it is demonstrated that the residence time must be larger than z/w and smaller than h/w, where z, h and w denote the distance to the pycnocline, the thickness of the mixed layer and the sinking velocity. In the vicinity of the pycnocline, the residence time is not necessarily zero; its behaviour critically depends on the eddy diffusivity profile in this region. Closed-form solutions are obtained for constant and quadratic diffusivity profiles, which allows for an analysis of the sensitivity of the residence time to the Peclet number. Finally, an approximate value is suggested of the depth-averaged value of the residence time.     

Persistent organic pollutants in Detroit River suspended sediments: polychlorinated dibenzo-p-dioxins and dibenzofurans,dioxin-like polychlorinated biphenyls and polychlorinated naphthalenes

Suspended sediments from the Detroit River were collected in 1999 and 2000 using sediment traps at sites ranging from western Lake Erie to southern Lake St. Clair and analyzed to determine the spatial distributions of contaminants including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs), dioxin-like PCBs (DLPCBs) and polychlorinated naphthalenes (PCNs). Concentrations of all three contaminant classes were clearly elevated at sites in the lower reaches of the river in the Trenton Channel. The potential influence of the Trenton Channel as a source of contamination to western Lake Erie was further evidenced by PCDD/PCDF homologue profiles, which indicated a contribution from chemical manufacturing in addition to the normal background combustion profile. Toxic equivalents (TEQs) for PCDDs/PCDFs generally exceeded those for DLPCBs; combined total TEQs in July 2000 for these two compound classes ranged from 2.30 pg/g in southern Lake St. Clair to 306 pg/g at a station just downstream of the outflow of Monguagon Creek in the Trenton Channel. The spatial distribution of PCN contamination was similar to that of PCDDs/PCDFs and DLPCBs, with the highest level of total PCNs (8200 ng/g) detected at a site in the Trenton Channel near Elizabeth Park; TEQs for PCNs in the Trenton Channel ranged from 73 to 3300 pg/g. The data indicate that PCNs represent a significant contribution to dioxin-like biological activity in Detroit River suspended sediments.