Neuroendocrine disruption and health effects in Elliptio complanata mussels exposed to aeration lagoons for wastewater treatment

The purpose of this study was to examine neuroendocrine-disrupting effects of two domestic wastewater aeration lagoons on freshwater mussels. Mussels were caged and placed in two final aeration lagoons for treating domestic wastewaters for 60 days, at a site 1km downstream of the dispersion plume on the eastern shores of the Richelieu River; the western shore served as the reference site. The mussels were analysed for gonad activity, oxidative metabolism of xenobiotics, stress biomarkers and neuroendocrine status (monoamine and arachidonic acid metabolism). The domestic wastewaters produced many different effects at all levels examined. The gonado-somatic index and vitellogenin-like proteins were significantly induced in both aeration lagoons and gonad pyrimidine synthesis (aspartate transcarbamylase activity) was significantly reduced, indicating that vitellogenin-like proteins were produced while DNA synthesis in gametes remained constant. Biomarkers of oxidative metabolism revealed that global heme oxidase (HO), glutathione S-transferase and xanthine (caffeine) oxydoreductase (XOR) activities were significantly induced in at least one of the aeration lagoons, but not downstream of the dispersion plume. The activities of 7-ethoxyresorufin (cytochrome P4501A1), dibenzoylfluorescein (cytochrome P450 3A4 and 3A5) and benzoyloxyresorurufin (cytochrome P450 3A4 and 2B6) dealkylases were readily induced by substances sharing structural similarities with coplanar polyaromatic hydrocarbons and hydroxylated or aminated aromatic or cyclic hydrocarbon compounds such as pharmaceuticals or steroids in the domestic wastewaters. Biomarkers of toxic stress revealed that exposure to aeration lagoons led to increased production of metallothioneins, lipid peroxidation and DNA strand breaks, with decreased heme oxygenase activity. LPO was significantly correlated with XOR, HO and cytochrome P4501A1 activities. Neuroendocrine effects included significant increases in dopamine and serotonin levels and in monoamine oxidase (MAO). Dopamine transport in synaptosome was significantly increased while serotonin transport activity was significantly decreased, suggesting the mussels were in a state of serotonergicity. Moreover, arachidonic acid cyclooxygenase (COX) activity was also readily increased in one aeration lagoon. Aeration lagoons for the treatment of domestic wastewaters are toxic, estrogenic and disrupt the metabolism of monoamines and COX in freshwater mussels.     

Polymer selection for passive sampling: a comparison of critical properties

Next to the bi-phasic semipermeable membrane devices (SPMDs), single-phase passive samplers are becoming more popular for the sampling of hydrophobic contaminants. We therefore evaluated some critical properties of 13 polymers: low-density polyethylene (LDPE), polyoxymethylene (POM), silicone rubbers (SRs), including polydimethylsiloxane, and ethylene/octene co-polymer (EXACT). Polymer comparison included four critical properties: release of oligomers, swelling in solvents (dichloromethane, hexane, ethyl acetate, acetone and methanol), contaminant diffusion coefficients and partition coefficients for naphthalene, fluoranthene, benzo[a]pyrene and dibenz[a,h]anthracene. Amounts of extracted oligomers ranged from 2% to 4% for SRs and LDPE, to about 1% for EXACT. No oligomer release was observed for POM. Diffusion coefficients were higher in all SRs compared with LDPE and EXACT. No measurable diffusion was observed in POM after 24h of exposure. Differences in polymer-water partition coefficients spanned two orders of magnitude, with the lowest values observed for POM and the highest values observed for LDPE and EXACT. For the ten tested SRs, this range was less than 0.4 log units. Transport resistances estimated on the basis of diffusion coefficients and partition coefficients were generally lower for SRs than for LDPE and EXACT.     

Polybrominated diphenyl ethers (PBDEs) in human milk from Australia

Polybrominated diphenyl ethers (PBDEs) are flame retardants added to a multitude of products to reduce flammability. PBDEs have been widely detected and quantified in biota and humans in many industrialised countries from the Northern Hemisphere. However data concerning the levels of these compounds in the Australian population and environment remain limited. The objectives of this study were to determine PBDE concentrations and congener profiles in Australian human milk and compare this to concentrations found in other countries. Pooled human milk samples obtained from mothers residing in 12 regions of Australia were analysed by HRGC/HRMS for 18 PBDE congeners. In total, 157 human milk samples collected in 2002 and 2003 were divided into 17 regional pools. PBDEs were detected in all pools of human milk from Australia. The mean+/-standard deviation and median summation operatorPBDE concentrations were 11.1+/-3.2 and 11.0 ng g(-1) lipid, respectively with a range of 6.1-18.7 ng g(-1) lipid. The congener profile was dominated by BDE-47 followed by BDE-99, -100, -153, -154 and -183. Regional differences were evaluated, but no trends were observed. The data suggest regional differences are likely to be small if they exist at all. The concentrations of PBDEs found in Australian human milk were lower than those reported from North America but higher than those reported from Europe and Asia. Our results suggest that the exposure pathways which contribute to the PBDE body burden in the Australian population require a better understanding in order to determine future policy regarding their use and disposal.     

Modifying sorbents in controlled release formulations to prevent herbicides pollution

The herbicides chloridazon and metribuzin, identified as groundwater pollutants, were incorporated in alginate-based granules to obtain controlled release properties. In this research the effect of incorporation of sorbents such as bentonite, anthracite and activated carbon in alginate basic formulation were not only studied on encapsulation efficiency but also on the release rate of herbicides which was studied using water release kinetic tests. In addition, sorption studies of herbicides with bentonite, anthracite and activated carbon were made. The kinetic experiments of chloridazon and metribuzin release in water have shown that the release rate is higher in metribuzin systems than in those prepared with chloridazon, which has lower water solubility. Besides, it can be deduced that the use of sorbents reduces the release rate of the chloridazon and metribuzin in comparison to the technical product and to the alginate formulation without sorbents. The highest decrease in release rate corresponds to the formulations prepared with activated carbon as a sorbent. The water uptake, permeability, and time taken for 50% of the active ingredient to be released into water, T(50), were calculated to compare the formulations. On the basis of a parameter of an empirical equation used to fit the herbicide release data, the release of chloridazon and metribuzin from the various formulations into water is controlled by a diffusion mechanism. Sorption capacity of the sorbents for chloridazon and metribuzin, ranging from 0.53mgkg(-1) for the metribuzin sorption on bentonite to 2.03x10(5)mgkg(-1) for the sorption of chloridazon on the activated carbon, was the most important factor modulating the herbicide release.     

Use of sulfadimethoxine in intensive calf farming: evaluation of transfer to stable manure and soil

After prophylactic treatment of 50 calves with 62mgkg(-1)day(-1) of sulfadimethoxine (SDM) for five days, the levels of the drug over time were followed in feces, bedding and stable manure, and then in the soil of a manured field and surrounding drainage courses. Analysis were done by HPLC after applying to the different matrices a quick and simple extraction procedure. The half-life of the drug in bedding was very short (24h). In stable manure the degradation rate of the drug slowed down and the calculated half-life was 64 days, with 390microgkg(-1) of SDM still detectable after three months maturation. However, in a five months matured stable manure obtained from other groups of calves subjected to the same prophylactic treatment, levels of SDM were <50muicrokg(-1) (LOD of the analytical method). After field fertilization with this manure, no traces of SDM were found in soil (LOD 10microgkg(-1)) or in the water (LOD 2microgl(-1)) from the surrounding drainage courses. Using the internationally recognised DAPHTOXKIT-Ftrade mark, a SDM toxicity test toward Daphnia magna was performed in the range 10-100mgl(-1). The test gave negative results both after 24 and 48h, confirming that microcrustaceans are less sensitive than other models to the toxicity of antibacterials. However, based on data from other authors, concerning algal toxicity and microbial inhibition, and on the analytical results from the current field study, the calculated worst-case EC50/PEC ratio for SDM both in freshwater and in soil was still >1000.     

Study of trace metal leaching from coals into seawater

The behaviour of three South African coals in water and, particularly in seawater, was examined. A sequential speciation procedure used to evaluate trace metal partitioning in coal has shown that trace metals will not be easily released from these coals into environmental ecosystems. Only a few trace elements are slightly leached from these coals into water or seawater at pH around 8. On the other hand, Mn is highly leached from these coals into water or seawater. It has been clearly shown that Mn concentrations are highly correlated to sulfate and calcium concentrations indicating that Mn is mainly solubilized into water simultaneously to gypsum; the leaching efficiency being severely reduced for coal having a high calcite content. The leaching percentage of Mn into seawater is enhanced by the presence of seawater salts that increases gypsum solubility. The leaching process of Mn from coal into water or seawater is governed by gypsum solubilization and is relatively rapid during the first thirty minutes, then very slow. In this study, it has been also shown that, depending on their physico-chemical properties, trace metals may be removed from seawater solutions in the presence of coal having a high calcite content. In this work, it has been also shown that some elements, particularly Fe, are greatly solubilized into seawater in the presence of a strong chelating agent like EDTA. Like for Mn, the leaching rate of metals from coal in the presence of EDTA is relatively rapid during the first 30 min then much slower, suggesting a solubilization process simultaneously to gypsum or/and calcite solubilization.     

Quantity and spectroscopic properties of soil dissolved organic matter (DOM) as a function of soil sample treatments: air-drying and pre-incubation

The dissolved organic matter (DOM) in soils is essentially defined by the way in which it is obtained. Therefore, we need to understand as to how pre-treatment of a soil will affect the characteristics of DOM, since this fraction may be strongly influenced by a soil's water content. The effect of two different pre-treatments on DOM from the A-horizons of a large variety of ecosystems and regions were compared. In both cases the soils were allowed to air-dry. In one case the air-dried soil was directly extracted (AD), while in the other case it was preincubated for 1 week at 50% of its water holding capacity (INCU). AD is simpler, but INCU brings the soil, and especially its microbial population, back to a standardised state, which is more representative of the usual state in the field. Both methods are used whenever an adjustment of the soil water content is essential to compare different regions or to eliminate short term weather effects. A significant regression indicated that the dissolved organic carbon (DOC) extracted from INCU samples was only 20% of AD DOC. Both the absorptivity (UV absorption divided by DOC) of 86% of the samples, and a fluorescence emission spectrum based Humification Index in all cases increased as a result of preincubation. This would indicate that labile compounds released during drying were metabolised during the incubation. However, the magnitude of this increase varied, and no correlation with soil organic and microbial carbon, pH, or texture could be detected. The results show that DOM extracted from AD and INCU soils is not comparable and that the differences are mainly due to the impact of air-drying on the microbial activity.     

Spatial variance in multimedia mass balance models: comparison of LOTOS-EUROS and SimpleBox for PCB-153

The aim of this study was to determine whether nested generic box models can be used to predict spatial variance. An inter-comparison study was performed for the nested box model SimpleBox, and the spatially resolved model LOTOS-EUROS, using PCB-153 emissions in Europe as an example. We compared the two models concerning (1) average environmental concentrations, (2) spatial concentration variances, (3) spatial concentration patterns (maps), and (4) agreement with measured concentrations for the air and soil compartments. In SimpleBox, the spatial concentration variances and patterns were calculated subsequently for each separate grid cell surrounded by a regional and a continental shell with homogeneous, averaged circumstances. Average European PCB-153 concentrations calculated by LOTOS-EUROS and SimpleBox for the period 1981-2000 agree well for the air and soil compartments. Moreover, the predicted concentrations of both models are in line with the measured PCB-153 concentrations in Europe during that period. For PCB-153, the prediction of spatial concentration variances with the nested multimedia fate model SimpleBox performs adequately in most cases, except for the lower concentration boundary in the air compartment. It is concluded that SimpleBox can be used to predict the spatial maximum and average concentrations of PCB-153 in the air and soil compartments. The proposed method has to be tested systematically for different types of compounds, emission scenarios, environmental compartments and spatial scales in order to allow conclusions about the general applicability of the method.     

Direct simulation of heterogeneous diffusion and inversion procedure applied to an out-diffusion experiment. Test case of Palmottu granite

An out-diffusion laboratory experiment using a non-reactive tracer was fitted using the Time Domain Diffusion (TDD) method. This rapid particle tracking method allows simulation of the heterogeneous diffusion based on pore-scale images and local values of diffusivities. The superimposed porosity and mineral 2D maps act as computation grids to condition diffusion pathways. We focused on a Palmottu granite sample, in which the connected pore space has a composite microstructure with cracks linking microporous minerals and is above the percolation threshold. Three main results were achieved: (i) When compared to the fitting obtained with one coefficient (best mean square residual R = 1.6 x 10(-2)), diffusion is shown to be suitably characterised with two coefficients related to cracks and microporous minerals (best R = 6.5 x 10(-4)), (ii) rather than imposing a local apparent diffusion coefficient D(a) independent of the local porosity Phi, a best fit is obtained by applying Archie's relationship D(a) = D(0) x G with G = Phi(m) to each pixel of the calculation grids (G is the geometry factor, D(0) is the diffusion coefficient in free fluid, and m is Archie's exponent), and (iii) the order of magnitude of the fitted diffusion coefficient or Archie's exponents (m=0 for microcracks and m=1.82 for microporous minerals) is physically realistic.