No abstract

This study evaluated the acute toxicity of sediment in a eutrophic reservoir after remediation with a calcium nitrate solution to retain phosphorus. The study involved microcosms of surface sediments and water from the sedimentwater interface in the Ibirité reservoir. This reservoir, located in the vicinity of metropolitan Belo Horizonte (Minas Gerais, SE Brazil), is a water body that receives treated effluents from an oil refinery (REGAP-Petrobras), as well as high loads of untreated urban effluents from the city of Ibirité and surrounding areas and industrial effluents from a major industrial park. Incubation times of the treatment experiments were: t = 0, t = 5, t = 10, t = 25, t = 50, t = 85 and t = 135 days. One control microcosm and three treated microcosms were analysed in each time interval. Acute toxicity of water samples was assessed with Ceriodaphnia silvestrii Daday, 1902 and that of bulk sediment samples with Chironomus xanthus Rempel, 1939. Toxicity tests were carried out concomitantly with chemical analyses of dissolved inorganic nitrogen species (ammonia, nitrate and nitrite), sulfate and metals in the water samples of the microcosms. Acid volatile sulfides (AVS), simultaneously extracted metal (SEM) and potentially bioavailable metal were analyzed in bulk sediment samples. Neither of the tested organisms showed toxicity in the control microcosm samples. The water column of the treated microcosm showed toxicity to C. silvestrii, starting at t = 10 days, while the sediment pore water toxicity started at t = 0 day. However, toxicity was found to decline from t = 85 days to t = 135 days. Sediments showed toxicity to C. xanthus during the entire experiment, except at the longest incubation time (t = 135 days). The overall results indicate that nitrate, which reached concentrations exceeding 1,200 mg N-NO 3 -L -1 in the sediment pore water of the treated microcosms, was most probably responsible for the toxicity of the samples. Although the calcium nitrate technology proved effective in retaining phosphorus, promoting sediment oxidation via denitrification, from the ecotoxicological standpoint and under the experimental conditions of this study, the application of nitrate for remediation of the sediments in the Ibirité reservoir did not prove effective up to a period of 135 days of incubation. However, we presume that after longer periods of incubation, treated sediments may recover their ability to sustain a benthic community. More advanced experiments are planned involving longer incubation times, thus extending the denitrification process, which may lead to a higher phosphorus retention capacity and to more complete abatement of sediment toxicity. Keywords

Although the Ibirité reservoir (an urban tropical eutrophic reservoir) has been the recipient of the discharge of a large volume of raw urban sewage, the key cause of ecosystem degradation has been historically solely attributed to the discharge of effluents from an oil refinery. This fact motivated an investigation to unravel the compositions of contaminants in the sediments to evaluate their distributions, possible sources, and potential impacts on sediment–water quality. The concentrations of polycyclic aromatic and aliphatic hydrocarbons and of metals and metalloids were, in general, significantly lower than some selected polluted sites used for comparison. Calculated distribution indexes showed that the hydrocarbon sources were petrogenic, pyrogenic, and biogenic. Only a few PAHs exceeded the threshold effects level (TEL) guideline. Industrial activities are the presumed sources of metals and metalloids except for copper, which is from copper sulfate used as algaecide in the reservoir. The bioavailable concentrations of some metal and metalloid exceeded the TEL–PEL guidelines. The acid volatile sulfide concentration was greater than that of the simultaneously extracted metals in the clayey–silty reservoir sediments, whereas the opposite result was observed for the sandy sediments of the tributaries. The sediment interstitial water toxic units were >1 for metals, thus indicating that metals are potentially toxic to the benthos. Considering the data set generated in this study, it can be concluded that the degradation of Ibirité reservoir and its tributaries cannot be solely attributed to the input of hydrocarbons, but predominantly to the discharge of raw urban sewage and effluents from other industrial sources.

This work presents the validation procedures of an analytical method to determine the 16 PAHs from the US EPA's priority pollutants list in sediment samples using ultrasonic extraction coupled to gas chromatography-mass spectrometry. The extraction techniques are altered by the construction of an extraction flask adapted to the ultrasonic bath that greatly reduces losses and increases extraction efficiency of the volatile compounds, especially naphthalene. Cleanup procedures are also altered to change the polarity of the solvent mixture that contributes to reducing the elution of undesirable compounds. The PAH spiked sediment at 100 microg/kg level shows recovery rate of 68% to 108%. A certified reference material has been analyzed for those compounds showing results conforming to certified values. The optimized procedure is applied to sediment samples from different areas across Southeast Brazil and presents the results from the Ibirité Reservoir (MG, Brazil), a eutrophic water body. The total PAH concentration in these sediment samples varies between 103.96 and 180.87 microg/kg (dry weight). As the detected concentrations are relatively low, the acute toxicity detected in sediment and its pore water is not due to these compounds, but to high concentrations of ammonia, copper, and nickel according to TIE procedures.