Analysis of Ah receptor pathway activation by brominated flame retardants

Brominated flame-retardants (BFRs) are used as additives in plastics to decrease the rate of combustion of these materials, leading to greater consumer safety. As the use of plastics has increased, the production and use of flame-retardants has also grown. Many BFRs are persistent and have been detected in environmental samples, raising concerns about the biological/toxicological risk associated with their use. Most BFRs appear to be non-toxic, however there is still some concern that these compounds, or possible contaminants in BFRs mixtures could interact with cellular receptors. In this study we have examined the interaction of decabromodiphenyl ether, Firemaster BP4A (tetrabromobisphenol A), Firemaster PHT4 (tetrabromophthalic anhydride), hexabromobenzene, pentabromotoluene, decabromobiphenyl, Firemaster BP-6 (2,2^′,4,4^′,5,5^′-hexabromobiphenyl) and possible contaminants of BFR mixtures with the Ah receptor. Receptor binding and activation was examined using the Gel Retardation Assay and increased expression of dioxin responsive genes was detected using the reporter gene based CALUX assay. The results demonstrate the ability of BFRs to activate the AhR signal transduction pathway at moderate to high concentrations as assessed using both assays. AhR-dependent activation by BFRs may be due in part to contaminants present in commercial/technical mixtures. This was suggested by our comparative analysis of Firemaster BP-6 versus its primary component 2,2^′,4,4^′,5,5^′-hexabromobiphenyl. Some technical mixtures of brominated flame-retardants contain brominated biphenyls, dioxins or dibenzofurans as contaminants. When tested in the CALUX assay these compounds were found to be equivalent to, or more active than their chlorinated analogues. Relative effective potency values were determined from dose response curves for these brominated HAHs.     

Metal biomonitoring with mosses: procedures for correcting for soil contamination

Highly variable total concentrations of 15 elements have been found in five species of epigeic mosses growing in remote areas of Italy and in northern Victoria Land (continental Antarctica). It is very likely that soil particles entrapped in the mosses cause these high element concentration differences, thereby leading to inexact interpretations of baseline concentrations and of element distribution in different parts of mosses. A simple procedure for estimating more plausible background values that consists of subtracting the substratum contribution from raw concentrations of elements in mosses is reported. The normalization of total concentrations to the regional soil composition is also emphasized, in order to point out other possible metal sources.     

A lysimeter experiment to investigate temporal changes in the availability of pesticide residues for leaching

Leaching of three pesticides (isoproturon, chlorotoluron and triasulfuron) and a tracer (bromide) were determined in four contrasting soils ranging in texture from sandy loam to clay. The compounds were applied to undisturbed columns of soil and four columns for each soil were randomly selected and leached with 24-mm equivalent of water at prescribed time intervals (3, 9, 24, 37 and 57 d after application). A rapid decline in leached loads of isoproturon and chlorotoluron as time from application to irrigation increased was observed in all soils. In contrast, triasulfuron and bromide loads only decreased rapidly in the clay soil. Bromide losses decreased with decreasing clay contents of the soil and therefore with a decrease in structural development. Magnitudes of pesticide losses varied from soil to soil, depending on structural development and the organic carbon content. Pesticide degradation experiments on disturbed and undisturbed soil samples showed that the rapid decline of leached loads with time was faster than could be explained by degradation alone. Five physico-chemical processes are put forward to explain the different patterns of pesticide leached loads observed in the soils: (1) relative extent of preferential flow, (2) sorption capacity of the compounds to the different soils, (3) extent of degradation of the compounds in the soil, (4) variation in sorption kinetics between compounds associated with pesticide diffusion into soil aggregates, and (5) protection of the compounds by a combination of intra-aggregate diffusion and the presence of preferential flow pathways.     

Humic acid enhanced remediation of an emplaced diesel source in groundwater. 1. Laboratory-based pilot scale test

The enhanced solubility of petroleum-derived compounds in humic acid solutions is the basis for a new groundwater remediation technology. In this unique pilot-scale test, a stationary contaminant source consisting of diesel fuel was placed below the water table in a model sand aquifer (1.2 x 5.5 x 1.8-m deep) and flushed with water at a flow rate of 2 cm/h over 5 years. At 51 days, laboratory grade humic acid was added to the water and maintained at a level of approximately 0.8 g/l. The addition of humic acid had only a small impact on the aqueous transport of the BTEX components, which were rapidly dissolved from the diesel, but had a large effect on the flushing of PAHs, including methylated naphthalenes (MNs). Binding to aqueous humic acid enhanced the solubilization of MNs two- to tenfold. During aqueous transport, biodegradation of the BTEX and PAHs occurred, limiting the lateral and longitudinal extent of the diesel contaminant plume in the model aquifer. It appears that through enhanced solubilization, the overall biodegradation rate of the MNs was increased. As the various MNs were depleted from the diesel source, the MN plume shrank and then disappeared.     

Preliminary Measurements of Turbulence and Environmental Parameters in a Sub-Tropical Estuary of Eastern Australia

In natural systems, mixing is driven by turbulence, but current knowledge is limited in estuarine zones where predictions of contaminant dispersion are often inaccurate. A series of detailed field studies was conducted in a small sub-tropical creek in eastern Australia. Hydrodynamic, physio-chemical and ecological measurements were conducted simultaneously to assess the complexity of the estuarine zone, notably the interactions between turbulence and environment. The measurements were typically performed at high frequency over a tidal cycle. The results provide an original data set to complement long-term monitoring and a basis for a more detailed study of mixing in sub-tropical systems. Unlike many long-term observations, velocity and water quality scalars were measured herein with sufficient spatial and temporal resolutions to determine quantities of interest in the study of turbulence, while ecological indicators were sampled systematically and simultaneously. In particular the results yielded contrasted outcomes, and the finding impacts on the selection process for key water quality indicators.     

Some biologically important low molecular weight organic acids in the sediments of Loch Eil

The isolation of biologically important low molecular weight organic acids from organically enriched sediments in Loch Eil, Scotland, was carried out by extraction of pore water with acidified ethyl acetate. High concentrations of acetic acid, up to 1.8 mg g^-1 dry weight of sediment were found at Station E-24. Propionate, butyrate, valerate, lactate and traces of succinate were also found. Succinate was present in significant amounts, 42.2 g g^-1 dry weight of sediment at Station E-70, which received a higher input of organic matter than E-24. Both propionate and succinate were absent from a control station in the Lynn of Lorne where the sediment was low in carbon compared with Loch Eil. In experimental tanks, acetate levels increased as the input of organic carbon (as cellulose) was increased up to a load level of 1.5 g m^-2 day^-1. Above this, acetate decreased and succinate appeared. Succinate was not detected in low-loaded tanks. Experiments with sieved mud showed a vertical distribution of the different acids with depth. Lactate and succinate reached highest concentration in the 0 to 3 cm layer, acetate at 3 to 6 cm and propionate at 6 to 9 cm. The results are discussed in relation to the role of these acids as food sources and as indicators of biochemical pathways taking place in sediments with different carbon input levels.     

Crop substitution in the estimation of economic benefits due to ozone reduction

Prior estimates of economic loss from ozone damage to food crops have not allowed for farmer substitution in inputs—and particularly have not allowed for acreage shifts between crops—in response to yield changes. This is a potentially serious problem since benefits from air pollution control legislation may also be estimated without allowing for this direct substitution. This study explores how much acreage shifting might occur between corn, soybeans, and wheat if ozone were reduced to background levels, and how such substitution might affect the estimation of benefits from ozone reduction.     

Designing an efficient adaptive cluster sample

The choice of neighborhood definition and critical value in adaptive cluster sampling is critical for designing an efficient survey. In designing an efficient adaptive cluster sample one should aim for a small difference between the initial and final sample size, and a small difference between the within-network and population variances. However, the two aims can be at odds with each other because small differences between initial and final sample size usually means small within-network variance. One way to help in designing an efficient survey is to think in terms of small network sizes since the network size is a function of both critical value and neighborhood definition. One should aim for networks that are small enough to ensure the final sample size is not excessively large compared with the initial sample size but large enough to ensure the within-network variance is a reasonable fraction of the population variance. In this study surveys that had networks that were two to four units in size were the most efficient.