Evidence of coprostanol estrogenicity to the freshwater mussel Elliptio complanata

Coprostanol (5 beta (H)-cholestan-3 beta ol) is a reduced metabolite of cholesterol produced by micro-organisms found in the intestinal tract of mammals. This substance abounds in urban effluents and is accumulated by organisms living in the vicinity of municipal effluent outfalls. In an earlier study, freshwater mussels exposed to contaminated river water for 62 days accumulated large quantities of coprostanol (Cop) in their soft tissues (16 micrograms/g dry wt.). Moreover, these mussels were found to have elevated levels of vitellin in their hemolymphs, suggesting estrogenic effects. Although municipal wastewaters are known to contain other estrogenic compounds capable of inducing Vn synthesis in mussels, the estrogenic potential of coprostanol was singled out for examination. To this end, mussels were first injected with concentrations of coprostanol via the abductor muscle route, and allowed to stand in aerated water for 72 h at 15 degrees C. The levels of Vn in mussel hemolymph were assayed using the organic alkali-labile phosphate method. A competitive estradiol-binding assay was then devised to measure the ability of coprostanol to compete in the binding of fluorescein-labeled estradiol-albumin to cytosolic proteins. Coprostanol partially reversed the binding of labeled estradiol-albumin to cytosolic proteins with an EC50 of 1 mM. In addition, injections of coprostanol and estradiol-17 beta led to increased levels of vitellins in the hemolymph of treated mussels. Moreover, incubation of cop in gonad homogenate extracts in the presence of NADPH led to the formation of two compounds, as determined by high-performance thin-layer chromatography. One of these compounds appears to be the C17 oxidation product of coprostanol, whose polarity is similar to that of estradiol. The results present evidence that coprostanol is estrogenic to freshwater mussels.     

Mineralogical compositions of aquifer matrix as necessary initial conditions in reactive contaminant transport models

Mineralogical compositions and their spatial distributions are important initial conditions for reactive transport modeling. However, popular Kd-based "reactive" transport models only require contaminant concentrations in the pore fluids as initial conditions, and minerals implicitly represent infinite sources and sinks in these models. That situation results in a general neglect of mineralogical characterization in site investigations. This study uses a coupled multi-component reactive mass transport model to predict the natural attenuation of a ground water plume at a uranium mill tailings site in western USA. Numerous ground water geochemistry data are available at this site, but mineralogical data are sketchy. Even given the well-defined pore fluid chemistry, variations of secondary mineral species and mineral abundances in the aquifer resulted in significantly different modeling outcomes. Results show that the amount of calcite in the aquifer determines the distances of plume migration. The possible presence of jurbanite, an aluminum sulfate phase, can store acidity temporarily but cause more severe contamination on a later date. The surfaces of iron oxyhydroxides can store significant amounts of sulfate and protons and serve as a second source for prolonged contamination. These simulations under field conditions illustrate that mineralogical compositions are an essential requirement for accurate prediction of contaminant fate and transport.     

On the hydro-dispersive equivalence between multi-layered mineral barriers

In the context of municipal solid waste and hazardous waste disposal, the notion of "equivalence" between different barrier designs appears in regulatory documents from several industrialized countries. While in the past, equivalence has been thought of mainly in terms of contaminant travel times, in recent years it has been defined more in terms of the magnitude of a disposal site's potential impact on groundwater resources. This paper presents some original analytical solutions to the problem of contaminant migration through a multi-layered mineral barrier. The solutions account for the two major mechanisms of subsurface contaminant migration, namely, advection and diffusion-dispersion. An example application using the proposed solutions and a numerical model illustrates how one multi-layered mineral barrier can be considered superior to another from a strictly hydro-dispersive viewpoint. The influence of partial saturation of the mineral barrier is investigated using a numerical solution to the Richards equation for unsaturated flow. It is emphasized that conclusions relative to the superiority of one multi-layered barrier, with respect to another, should not only consider hydro-dispersive aspects, but also other processes such as the mechanical and chemical evolutions of the different barrier components. Although such phenomena are poorly addressed by existing models, failure to take them into account, at least in a qualitative fashion, may lead to unconservative conclusions with respect to barrier equivalence.     

Seasonal variations in phosphorus species in the surface sediments of the Gulf of Riga, Baltic Sea.

The redox-dependent variations in concentrations of phosphorus at two different accumulation bottom areas were investigated in the Gulf of Riga (Baltic Sea) between December 1993 and January 1995. The sediment samples from nine sampling occasions were analyzed for phosphorus forms and redox potential. The average concentrations of total phosphorus measured in 0-1 cm (65 and 89 micromol P g(-1) for sites G5 and T3, respectively) were among the highest reported from the entire Baltic Sea. Redox-dependent "mobile" phosphorus (MP) contributed more than 50% of total in the uppermost-oxidized centimeter, whereas in reduced layers it was 16-18% throughout the year. The significant differences (ANOVA, P<0.01) among months of inorganic phosphorus (IP) concentration at 0-1 cm were observed at site G5 due to temporary accumulation of mobile phosphorus mediated by redox-dependent bacteria activity during summer. On the contrary no accumulation was observed at T3 probably as a result of low redox potential caused by high accumulation rates and low bioturbation. Although the water column above sediments remained oxic throughout the investigation period, the redox potential at site T3 was close to the redoxcline (i.e., +230 mV) during summer. Further increase of eutrophication might lead to development of anoxic conditions at sediment-water interface and that in turn will result in rapid release of redox-dependent phosphorus stored in surface sediments. The availability of excess phosphorus will further enhance eutrophication in partly phosphorus-limited Gulf of Riga.     

Metals in sediments and the edible cockle Cerastoderma edule from two Moroccan Atlantic lagoons: Moulay Bou Selham and Sidi Moussa.

Metals (Cd, Cu, Pb and Zn) were determined over a 3-year period in sediments and bivales Cerastoderma edule from two lagoon ecosystems on the Moroccan Atlantic coastline, Moulay Bou Selham and Sidi Moussa. Sediment metal concentrations were seasonally influenced, and were highest, generally, in winter--possibly signifying an increased contribution from run-off from adjacent arable land and roads. Neither site can be considered highly contaminated; however, Cd was enriched at Sidi Moussa, probably as a result of waste discharge from phosphate industries 20 km along the coast to the northeast. This ability to act as a sink for metals at distance from sources demonstrates the need for surveillance in these sensitive environments. Copper and Zn concentrations in edible cockles C. edule appear to be regulated over the concentration ranges currently found in lagoon sediments. In contrast, body burdens of Pb and, to a lesser extent Cd, reflect sediment levels and might be useful in future risk assessments. Metal concentrations Cerastoderma edule are seasonally related to the reproductive cycle, however, and sample timing will need to be standardised in future monitoring exercises.     

Microcosm studies of microbial degradation in a coal tar distillate plume

Investigation of a groundwater plume containing up to 24 g l(-1) phenolic compounds suggested that over a period of nearly 50 years, little degradation had occurred despite the presence of a microbial community and electron acceptors within the core of the plume. In order to study the effect of contaminant concentration on degradation behaviour, laboratory microcosm experiments were performed under aerobic and anaerobic conditions at four different concentrations obtained by diluting contaminated with uncontaminated groundwater. The microcosms contained groundwater with total phenols at ca. 200, 250, 660 and 5000 mg l(-1), and aquifer sediment that had been acclimatised within the plume for several months. The microcosms were operated for a period of 390-400 days along with sterile controls to ascertain whether degradation was microbially mediated or abiotic. Under aerobic conditions, degradation only occurred at concentrations up to 660 mg l(-1) total phenols. At phenol concentrations below 250 mg l(-1) a benzoquinone intermediate, thought to originate from the degradation of 2,5-dimethylphenol, was isolated and identified. This suggested an unusual degradative pathway for this compound; its aerobic degradation more commonly proceeding via catecholic intermediates. Under anaerobic conditions, degradation only occurred in the most dilute microcosm (total phenols 195 mg l(-1)) with a loss of p-cresol accompanied by a nonstoichiometric decrease in nitrate and sulphate. By inference, iron(III) from the sediment may also have been used as a terminal electron acceptor, in which case the amount of biologically available iron released was calculated as 1.07 mg Fe(III)/g of sediment. The study shows that natural attenuation is likely to be stimulated by dilution of the plume.     

Economic comparison of emission control systems for glass manufacturing furnaces with heat recovery

Glass manufacturing, like other process industries, is faced with air pollution compliance problems due to ever stricter emission limits. Several waste gas cleaning equipment options are available for air pollution control (APC) in glass plants, the most common arrangements being based on electrostatic precipitator (ESP) or fabric filter (FF) dust collectors and semi-wet or dry processes for acid gas removal. However, several counteracting aspects affect the choice of gas cleaning technologies, which are confirmed by the discrepancies encountered in actual suppliers' bids. In this paper, the main pollution control options are analyzed by carrying out a critical comparison under the cost-effectiveness point of view to select the lowest cost arrangement considering capital investment, operating expenses, and energy-saving revenues from heat recovery processes. The analysis is carried out with reference to a case study involving actual float glass production lines at Pilkington plants in Italy.     

Analysis of the relationship between ambient levels of O3, NO2 and NO as a function of NOx in the UK

Monitoring data from the UK Automatic Urban and Rural Network are used to investigate the relationships between ambient levels of ozone (O₃), nitric oxide (NO) and nitrogen dioxide (NO₂) as a function of NO_x, for levels ranging from those typical of UK rural sites to those observed at polluted urban kerbside sites. Particular emphasis is placed on establishing how the level of ‘oxidant’, OX (taken to be the sum of O₃ and NO₂) varies with the level of NO_x, and therefore to gain some insight into the atmospheric sources of OX, particularly at polluted urban locations. The analyses indicate that the level of OX at a given location is made up of NO_x-independent and NO_x-dependent contributions. The former is effectively a regional contribution which equates to the regional background O₃ level, whereas the latter is effectively a local contribution which correlates with the level of primary pollution. The local oxidant source has probable contributions from (i) direct NO₂ emissions, (ii) the thermal reaction of NO with O₂ at high NO_x, and (iii) common-source emission of species which promote NO to NO₂ conversion. The final category may include nitrous acid (HONO), which appears to be emitted directly in vehicle exhaust, and is potentially photolysed to generate HO_x radicals on a short timescale throughout the year at southern UK latitudes. The analyses also show that the local oxidant source has significant site-to-site variations, and possible reasons for these variations are discussed. Relationships between OX and NO_x, based on annual mean data, and fitted functions describing the relative contributions to OX made by NO₂ and O₃, are used to define expressions which describe the likely variation of annual mean NO₂ as a function of NO_x at 14 urban and suburban sites, and which can take account of possible changes in the regional background of O₃.     

Resistant sorption of in situ chlorobenzenes and a polychlorinated biphenyl in river Rhine suspended matter

The desorption kinetics of in situ chlorobenzenes (dichlorobenzenes, pentachlorobenzene and hexachlorobenzene) and 2,4,4^′-trichlorobiphenyl (PCB-28) were measured with a gas-purge technique for river Rhine suspended matter sampled in Lobith, The Netherlands. This suspended matter is the main source of sediment accumulation in lake Ketelmeer. In lake Ketelmeer sediment earlier observations showed that slow and very slow fractions dominate the desorption profile.

For the river Rhine suspended matter, only for PCB-28 a fast desorbing fraction of around 1.6% could be detected. The observed rate constants were on the average 0.2 h⁻¹ for fast desorption, 0.004 h⁻¹ for slow desorption, and 0.00022 h⁻¹ for very slow desorption. These values are in agreement with previous findings for the sediment from lake Ketelmeer and with available literature data on fast, slow, and very slow desorption kinetics.

The results from this study show the similarity of desorption profiles between river Rhine suspended matter, and the top layer sediment from lake Ketelmeer. This indicates that slow and very slow fractions are already present in material forming the top layer of lake Ketelmeer, and were not formed after deposition of this material in the lake. The absence of detectable fast fractions for most compounds could be caused by the absence of recent pollution of the suspended matter. But, the observations may also be explained by a rapid disappearance of compounds from the fast fraction due to a combination of a high affinity of very slow sites for these compounds, and their relatively high volatility.     

Baseline levels of PCDD/Fs in soil and herbage samples collected in the vicinity of a new hazardous waste incinerator in Catalonia,Spain

The construction in Constantí (Catalonia, Spain) of a new hazardous waste incinerator (HWI), which is the first one in Spain, finished in 1999. In order to determine the temporal variation (1996–1998) in the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the vicinity of the new HWI, 40 soil and 40 herbage samples were collected (1998) at the same sampling points in which samples had been taken two years before (1996). Each sample was analyzed for PCDDs and PCDFs by high resolution gas chromatography/high resolution mass spectrometry. In the 1996 survey, PCDD/F concentrations in soils ranged from 0.13 to 24.20 ng I-TEQ/kg (d.m.), with median and mean values of 0.67 and 1.68 ng I-TEQ/kg (d.m.), respectively. In the present study, PCDD/F concentrations ranged from 0.12 to 17.20 ng I-TEQ/kg (d.m.), with a median value of 0.75 ng I-TEQ/kg (d.m.) and a mean value of 1.59 ng I-TEQ/kg (d.m.). In turn, in the present study PCDD/F concentrations in vegetation ranged from 0.14 to 2.01 ng I-TEQ/kg (d.m.) (median and mean values: 0.23 and 0.31 ng I-TEQ/kg, respectively), while in the 1996 survey PCDD/F concentrations ranged from 0.24 to 1.22 ng I-TEQ/kg (d.m.) (median and mean values: 0.53 and 0.61 ng I-TEQ/kg, respectively). According to the present (1998) and the previous (1996) levels of PCDD/Fs found in soils and vegetation, the area under potential influence of the new facility shows a rather low contamination by these compounds. The current results should be useful to establish the environmental impact of the HWI.