Assessment of organic and inorganic contaminants in sediments of an urban tropical eutrophic reservoir

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.     

Application of Fenton, photo-Fenton, solar photo-Fenton, and UV/H2O2 to degradation of the antineoplastic agent mitoxantrone and toxicological evaluation

In the present study, selected advanced oxidation processes (AOPs)—namely, photo-Fenton (with Fe²⁺, Fe³⁺, and potassium ferrioxalate—FeOx—as iron sources), solar photo-Fenton, Fenton, and UV/H₂O₂—were investigated for degradation of the antineoplastic drug mitoxantrone (MTX), frequently used to treat metastatic breast cancer, skin cancer, and acute leukemia. The results showed that photo-Fenton processes employing Fe(III) and FeOx and the UV/H₂O₂ process were most efficient for mineralizing MTX, with 77, 82, and 90 % of total organic carbon removal, respectively. MTX probably forms a complex with Fe(III), as demonstrated by voltammetric and spectrophotometric measurements. Spectrophotometric titrations suggested that the complex has a 2:1 Fe³⁺:MTX stoichiometric ratio and a complexation constant (K) of 1.47 × 10⁴ M^–1, indicating high MTX affinity for Fe³⁺. Complexation partially inhibits the involvement of iron ions and hence the degradation of MTX during photo-Fenton. The UV/H₂O₂ process is usually slower than the photo-Fenton process, but, in this study, the UV/H₂O₂ process proved to be more efficient due to complexing of MTX with Fe(III). The drug exhibited no cytotoxicity against NIH/3T3 mouse embryonic fibroblast cells when oxidized by UV/H₂O₂ or by UV/H₂O₂/FeOx at the concentrations tested.     

Evaluation of optimal conditions for determination of low selenium content in shellfish samples collected at Todos os Santos Bay,Bahia, Brazil using HG-AFS

This work proposes a procedure for the determination of total selenium content in shellfish after digestion of samples in block using cold finger system and detection using atomic fluorescent spectrometry coupled hydride generation (HG AFS). The optimal conditions for HG such as effect and volume of prereduction KBr 10 % (m/v) (1.0 and 2.0 ml) and concentration of hydrochloric acid (3.0 and 6.0 mol L^?1) were evaluated. The best results were obtained using 3 mL of HCl (6 mol L^?1) and 1 mL of KBr 10 % (m/v), followed by 30 min of prereduction for the volume of 1 mL of the digested sample. The precision and accuracy were assessed by the analysis of the Certified Reference Material NIST 1566b. Under the optimized conditions, the detection and quantification limits were 6.06 and 21.21 μg kg^?1, respectively. The developed method was applied to samples of shellfish (oysters, clams, and mussels) collected at Todos os Santos Bay, Bahia, Brazil. Selenium concentrations ranged from 0.23?±?0.02 to 3.70?±?0.27 mg kg^?1 for Mytella guyanensis and Anomalocardia brasiliana, respectively. The developed method proved to be accurate, precise, cheap, fast, and could be used for monitoring Se in shellfish samples.     

Ecological Status of a Margaritifera margaritifera (Linnaeus, 1758) Population at the Southern Edge of its Distribution (River Paiva, Portugal)

An important population of the critically endangered pearl mussel Margaritifera margaritifera (Linnaeus, 1758) was surveyed at the edge of its southern distribution (River Paiva, Portugal). Although an earlier study suggested that this population had a very low number of individuals (<500), a narrow distribution, and was mainly comprised by old specimens our data contradict these findings. Our assessment estimated a population with probably more than 5,000 individuals distributed across 80 km of the river length. From the 32 sites surveyed, 19 contained M. margaritifera with higher abundances verified in the middle and upper parts of the river (a maximum of 78 ind. per 100 m of river stretch was recorded). The pearl mussels showed a clear preference for areas near the banks, in shallow water, sandier and gravel sediments, and a high degree of riparian vegetation cover. The population structure was skewed with a very high percentage of large (and old) animals but 3.7 % of the individuals collected were juveniles (<60 mm in length); therefore, this population can be considered functional. Environmental characterization indicated that this river is still in excellent or good condition although some areas showed deterioration due to discharge of domestic effluents. The main conservation requirements of M. margaritifera in the River Paiva include maintaining the water quality (and if possible stopping the discharge of domestic effluents), increasing riparian vegetation cover, removing several weirs to increase connectivity, and increasing trout density.     

Evolutionary strategies of chemical defense in aposematic butterflies: Cyanogenesis in Asteraceae-feeding American Acraeinae

Summary American Acraeinae butterflies often ingest large amounts of dehydropyrrolizidine alkaloids (PAs) from their Asteraceae hostplants in both larval and adult stages, but do not normally store these compounds for defence, instead biosynthesizing large amounts of the cyanogenic glucoside linamarin in all stages. This defence syndrome (rejection of plant toxins andde novo synthesis of protective chemicals) is considered to be the most evolved among aposematic (unpalatable mimicry-model) butterflies, as are the Acraeinae and Heliconiini which also synthesize cyanogens. Storage or minimal processing of larval hostplant-derived defensive chemicals is widespread and characterizes the most primitive model groups; an intermediate series (Danainae/Ithomiinae) also obtains the principal defensive chemicals (PAs) from plants, but mostly in the adult stage. These syndromes are discussed and contrasted with the pattern seen in Chrysomelidae beetles, wherede novo synthesis is widespread and considered primitive.Originally presented at the 9th Meeting on Micromolecular Evolution, Systematics and Ecology (Ribeirão Preto, SP, April 1987); see also Brownet al. (1990)     

Risk of exposure to Hg and pesticides residues in a traditional fishing community in the Amazon: a probabilistic approach based on dietary pattern

Exposure to mercury (Hg) and pesticides (o.p’DDT, p.p’DDT, o.p’DDE, and p.p’DDE) in the Amazon through eating fish is of concern due to the large participation of this food in the diet of traditional fishing communities. The aim of this study was to evaluate the estimated daily intake (EDI) and the incremental lifetime cancer risk associated with Hg and o.p’DDT, p.p’DDT, o.p’DDE, and p.p’DDE in an Amazonian community. The results showed that for Hg, the EDI from carnivorous and detritivorous fish had the highest values, while for pesticides, the EDI from detritivorous fish intake had the highest value. The incremental lifetime cancer risk was below the permitted limit. A recommendation for controlling the high risk of exposure includes the reduction of detritivorous fish ingestion and/or replacement with herbivorous fish, which had lower EDI. We highlight the importance of investigating the human dietary patterns when estimating risk of exposure to Hg and pesticides.