Concentrações e associações geoquímicas de Pb e Zn em sedimentos do rio São Francisco impactados por rejeitos da produção industrial de zinco

Surface sediments from the River São Francisco were analyzed to investigate the impact, due to the presence of metals (Cd, Cu, Pb, Zn) in wastes from a metallurgical industry in the city of Três Marias/MG, Brazil. The concentrations and geochemical associations of Pb, Zn and trace metals associated with the minerals employed in zinc production were measured. Sediments close to discharge locations were highly contaminated with Pb (332-512 μg g-1) and Zn (7872-10780 μg g-1), with values decreasing rapidly due to dilution and hydraulic sorting. Evaluation of toxicity according to the Consensus-based Sediment Quality Guidelines indicated for Cd, Pb and Zn a high probability of adverse effects on aquatic biota at these sites.

Bioconcentração e biomagnificação de metilmercúrio na baía de Guanabara, Rio de Janeiro

Methylmercury was determined in water and aquatic biota from Guanabara Bay. Trophic transfer of methylmercury was observed between trophic levels from prey (microplankton, mesoplankton and fish with different feeding habits) to top predator (pelagic demersal fish). Top predator fish presented the highest methylmercury concentrations (320.3 ± 150.7 mg kg-1 dry wt.), whereas microplankton presented the lowest (8.9 ± 3.3 mg kg-1 dry wt.). The successive amplification of methylmercury concentrations and its bioconcentration factor with increasing trophic levels from base to top indicate that biomagnification may be occurring along the food web. Results suggest the importance of feeding habits and trophic level in the bioaccumulation of methylmercury by aquatic biota.

Caracterização estrutural das substâncias húmicas aquáticas extraídas dos rios itapanhaú e ribeira de iguape

The knowledge of the structure characteristic of the Organic Matter is important for the understanding of the natural process. In this context aquatic humic substances (principal fraction) were isolated from water sample collected from the two distinct rivers, using procedure recommended for International Humic Substances Society and characterized by elemental analysis, electron paramagnetic resonance and nuclear magnetic resonance (13C NMR). The results were interpreted using principal component analysis (PCA) and the statistical analyses showed different in the structural characteristics of the aquatic humic substances studied.

Análise de risco de contaminação de águas superficiais e subterrâneas por pesticidas em municípios do Alto Paranaíba - MG

A preliminary analyses of the possible contamination of surface and groundwater by the active ingredients of the pesticide products used in the areas with intensive agricultural activities of Alto Paranaíba region, MG, Brazil, was carried out. The active ingredients and formulated products most used in the region were identified and their characteristics of environmental importance were presented. The EPA screening criteria, the groundwater ubiquity score (GUS) and the criteria proposed by Goss were used to evaluate which pesticides might contaminate the local waters. Among the active ingredients studied, several present risks to the local aquatic environment.

Sulfetos volatilizáveis por acidificação e metais extraídos simultaneamente na avaliação de sedimentos de água doce

This paper discusses the historical and methodological fundaments of the dynamics and quantification of acid volatile sulfides (AVS) and simultaneously extracted metals (SEM) in aquatic sediments. It also discusses the SEM/AVS relationship, which involves several controversial aspects such as sulfide stability, sulfide-organic matter interaction, and the inability to predict the toxicity of organic compounds in the environment. This relationship is an important tool for the inference of metal bioavailability. The use of ecotoxicological tests with target organisms regulated by international standards is also a relevant aspect.

Coeficientes de difusão de metais em materiais não convencionais (agarose e acetato de celulose) usados na técnica de difusão em filmes finos por gradientes de concentração

The DGT technique allows one to measure quantitatively free and labile metal species in aquatic systems. Nevertheless, for this approach, knowledge is required of the diffusion coefficients of the analytes in a diffusive layer. In this study, the diffusion coefficients of Hg(II), As(III), Mn(II), Mg(II), Cu(II), Cd(II) were determined in agarose gel and those of Ba(II), Cd(II), Cu(II), Mg(II), Mn(II) e Zn(II) in cellulose acetate membranes. These materials presented good performance and the reported results can be used as a data base for further DGT studies.

Resíduos de pesticidas em águas superficiais de área de nascente do Rio São Lourenço-MT: validação de método por extração em fase sólida e cromatografia líquida

A multiresidue method using HPLC/DAD for the determination of fourteen pesticides in water based on SPE, using SDVB (styrene divynilbenzene copolymer) as adsorbent was validated. Recoveries from 61 to 120%, relative standard deviation between 2 and 15% and detection limits from 0.07 to 0.75 µg L-1 were obtained. It was applied to 66 surface water samples collected in a degraded area at the headwaters of São Lourenço river, Mato Grosso, Brazil. Eight pesticides were detected in concentrations ranging from 0.15 to 35.25 µg L-1. Considering ecotoxicological data, carbendazim and carbofuran may represent a risk to aquatic organisms. These results draw attention to the contamination of this vulnerable degraded area.

Avaliação de risco ambiental de ambientes aquáticos afetados pelo uso de agrotóxicos

Ecological risk assessment is a process evaluating the likelihood that adverse ecological effects may occur or are occurring as a result of exposure to one or more substances. Relevant information needed to predict risks from pesticides includes their physical chemical properties, mobility in soil, persistence in the environment, and bioaccumulation and toxicity in relevant organisms. Although currently a requirement for pesticide registration in Brazil, this process is not yet fully implemented in the country. This review aims to outline the principles of environmental risk assessment for pesticides, focusing on aquatic organisms, and to discuss the studies and efforts conducted in Brazil in this area.

Adsorptive removal of harmful organic compound from aqueous solutions

Adsorption is one of the most commonly used methods in water treatment processes. It is attractive due to it easy operation and the availability of a wide variety of commercial adsorbents. This doctoral thesis focuses on investigating and explaining the influence of external phase conditions (temperature, pH, ionic strength, acidity, presence of cosolutes) on adsorption phenomena. In order to cover a wide range of factors and phenomena, case studies were chosen from various fields where adsorption is applied. These include the adsorptive removal of surface active agents (used in cleaning chemicals, for example) from aqueous effluents, the removal of hormones (estradiol) from drinking water, and the adsorption of antibiotics onto silica. The latter can beused to predict the diffusion of antibiotics in the aquatic system if they are released into the environment. Also the adsorption of living cells on functionalized polymers to purify infected water streams was studied. In addition to these examples, the adsorptive separation of harmful compounds from internal water streams within a chemical process was investigated. The model system was removal of fermentation inhibitors from lignocelluloses hydrolyzates. The detoxification of the fermentation broth is an important step in the manufacture of bioethanol from wood, but has not been studied previously in connection with concentrated acid hydrolyzates. New knowledge on adsorption phenomena was generated for all of the applications investigated. In most cases, the results could be explained by combining classical theories for individual phenomena. As an example, it was demonstrated how liquid phase aggregation could explain abnormal-looking adsorption equilibrium data. In addition to the fundamental phenomena, also process performance was of interest. This aspect is often neglected in adsorption studies. It was demonstrated that adsorbents should not be selected for a target application based on their adsorption properties only, but regeneration of the spent adsorbent must be considered. It was found that using a suitable amount of organic co-solvent in the regeneration can significantly improve the productivity of the process.

Riparian vegetation affected by bank erosion in the Lower São Francisco River, Northeastern Brazil

Changes in the hydrological regime of the Lower São Francisco River, located in Northeastern Brazil have brought negative environmental impacts, jeopardizing the flora and fauna of a global biodiversity hotspot, due to implementation of hydroelectric power dams and surface water withdrawal for irrigation in public and private perimeters. Remnants of the riparian stratum associated to the riverbank destabilization in six fragments were studied by surveying trees, shrubs, herbs, and aquatic species. The calculation of the Factor of Safety (FS) was performed in order to understand the riverbank's stability related to soil texture and vegetation cover. An overall number of 51 botanic families distributed in 71 genera and 79 species were recorded, predominantly from the families Mimosaceae, Myrtaceae, and Fabaceae. The fragmented riparian vegetation is mostly covered by secondary species under a strong anthropogenic impact such as deforestation, mining and irrigation, with an advanced erosion process in the river margins. Strong species that withstand the waves present in the river flow are needed to reduce the constant landslides that are mainly responsible for the river sedimentation and loss of productive lands. A lack of preservation attitude among the local landholders was identified, and constitutes a continuing threat to the riparian ecosystem biodiversity.

Removal of organic matter and nutrients from slaughterhouse wastewater by using Eichhornia crassipes and evaluation of the generated biomass composting

The objective of this research was to evaluate the performance of the aquatic macrophyte Eichhornia crassipes applied in situ in a slaughter house treatment system, located in the west of the Paraná state, Brazil, regarding the nutrients removal and organic matter. Moreover, it aimed to obtain data from the production, management and composting practices of the biomass generated in the system. During 11 months of macrophytes development, physic and chemical parameters were monitored and plant density was controlled by periodical removal of excess biomass, which was weekly monitored and it is expressed in kg of aquatic plant per m² covered area. The degradation of the macrophytes removed from the treatment system was evaluated at the pilot scale in eight composting piles of 0.60 m³ that underwent four different treatments and two repetitions: T1 - water hyacinth (Eichhornia crassipes); T2 - water hyacinth and swine excrement (7:1), T3 - water hyacinth, swine excrement and earth (7:1:0,67), and T4 - water hyacinth, swine excrement and cellulosic gut (7:1:0,67), for a period of 90 days. The results indicated maximum removal efficiencies of 77.2% for COD; 77.8% for BOD, 87.9% for total nitrogen, 47.5% for ammonia nitrogen and 38.9% for total phosphorus for a five-day retention time. For biomass stabilization by composting, considering the C:N ratio as an indicator of compost maturity, it was observed that treatment T4 resulted in the shortest stabilization period (60 days). No difference was verified in the biostabilization rates at 5% level by the F test.

Vesirakentamisen ja säännöstelyn sekä niihin liittyvien kompensaatiotoimenpiteiden vaikutukset Kalajoen kala-, nahkiais- ja rapukantoihin : Yhteenveto vuosien 1978-2010 velvoitetarkkailujen tuloksista

Kalajoen pääuomassa on tehty suuria vesistöjärjestelyjä 1900-luvun alusta aina 2000-luvulle asti. Jokiuomaa ja sen virtaamia on muutettu mm. tulvasuojelun, voimatalouden ja uiton edistämiseksi. Merkittävimmät vesistöjärjestelyt ovat olleet Kalajoen säännöttäminen vuosina 1903–1910, Niemelänkylän pengerrys vuosina 1955–1960, Kalajoen vesistötaloussuunnitelma 1960–1970-luvulla, Kalajoen keskiosan järjestely vuosina 1967–1988, Alavieskan tulvasuojelu vuosina 1990–1992 ja Juurikosken kunnostus vuosina 2004–2005. 1970-luvunlopulta lähtien vesistöjärjestelyiden lupamääräyksiin alettiin sisällyttää velvoitteita tarkkailla hankkeiden vaikutuksia veden laatuun, kalastoon ja kalastukseen. Lisäksi aiheutetun haitan kompensoimiseksi alettiin määrätä toimenpiteitä, kuten kalaistutuksia ja kunnostustoimenpiteitä. Lupamääräykset ovat sisältäneet myös velvoitteita tarkkailla kompensaatiotoimenpiteiden tuloksellisuutta. Kalajoella valtio on ollut selvästi merkittävin toimija vesistöjärjestelyissä ja on ollut luvanhaltijana pääosassa hankkeista. Lisäksi valtio on kaikkien Kalajoen vesistön säännöstelyjen luvanhaltija. Näin ollen valtio on vastannut myös hankkeisiin liittyvistä velvoitetarkkailuista ja kompensaatiotoimenpiteistä. Merkittävimmät kompensaatiotoimenpiteet ovat olleet 4,7 miljoonan yksikesäisen vaellussiian istuttaminen vuosina 1981–2010, Kalajoen kunnostaminen mm. ravun ja nahkiaisen lisääntymisedellytysten parantamiseksi vuosina 1999–2004 ja 30 000 sukukypsän ravun istuttaminen vuosina 2003–2006. Tässä raportissa on tehty yhteenveto Kalajoen tarkkailututkimuksista vuosilta 1978–2010. Niiden perusteella on arvioitu, kuinka vesistörakentamishankkeet ja säännöstely sekä niihin liittyvät kompensaatiotoimenpiteet ovat vaikuttaneet rapu-, nahkiais- ja kalakantoihin sekä Kalajokeen niiden elinympäristönä. Lisäksi käytettävissä olevan aineiston puitteissa on arvioitu muiden tekijöiden vaikutusta rapu-, nahkiais- ja kalakantoihin.

Main diseases of pejerrey (Odontesthes bonariensis) in central Argentina

Argentina's central region includes an important area covered by shallow pampean lakes and dams. In these environments, fishing of pejerrey Odontesthes bonariensis Valenciennes, 1835 (Pisces, Atherinopsidae), the most important fresh-water fish of the country, is a relevant social activity and also a considerable economic resource. The main diseases found in this species were studied from 1992 to 2003 in the provinces of Córdoba, La Rioja and Santa Fe (30º and 35º S, 61º and 67º W). Most cases were registered in high temperature months. Lernaea sp and Aeromonas hydrophila were the etiological agents most frequently found. The trophic characteristics of the aquatic environments enhanced disease processes and caused massive death of O. bonariensis, due to complex hydrochemical interactions.

Biodiversity and ecosystem functioning in angiosperm communities in the Baltic Sea

The biological variation in nature is called biodiversity. Anthropogenic pressures have led to a loss of biodiversity, alarming scientists as to what consequences declining diversity has for ecosystem functioning. The general consensus is that diversity (e.g. species richness or identity) affects functioning and provides services from which humans benefit. The aim of this thesis was to investigate how aquatic plant species richness and identity affect ecosystem functioning in terms of processes such as primary production, nutrient availability, epifaunal colonization and properties e.g. stability of Zostera marina subjected to shading. The main work was carried out in the field and ranged temporally from weeklong to 3.5 months-long experiments. The experimental plants used frequently co-occur in submerged meadows in the northern Baltic Sea and consist of eelgrass (Z. marina), perfoliate pondweed (Potamogeton perfoliatus), sago pondweed (P. pectinatus), slender-leaved pondweed (P. filiformis) and horned pondweed (Zannichellia palustris). The results showed that plant richness affected epifaunal community variables weakly, but had a strong positive effect on infaunal species number and functional diversity, while plant identity had strong effects on amphipods (Gammarus spp.), of which abundances were higher in plant assemblages consisting of P. perfoliatus. Depending on the starting standardizing unit, plant richness showed varying effects on primary production. In shoot density-standardized plots, plant richness increased the shoot densities of three out of four species and enhanced the plant biomass production. Both positive complementarity and selection effects were found to underpin the positive biodiversity effects. In shoot biomass-standardized plots, richness effects only affected biomass production of one species. Negative selection was prevalent, counteracting positive complementarity, which resulted in no significant biodiversity effect. The stability of Z. marina was affected by plant richness in such that Z. marina growing in polycultures lost proportionally less biomass than Z. marina in monocultures and thus had a higher resistance to shading. Monoculture plants in turn gained biomass faster, and thereby had a faster recovery than Z. marina growing in polycultures. These results indicate that positive interspecific interactions occurred during shading, while the faster recovery of monocultures suggests that the change from shading stress to recovery resulted in a shift from positive interactions to resource competition between species. The results derived from this thesis show that plant diversity affects ecosystem functioning and contribute to the growing knowledge of plant diversity being an important component of aquatic ecosystems. Diverse plant communities sustain higher primary productivity than comparable monocultures, affect faunal communities positively and enhance stability. Richness and identity effects vary, and identity has generally stronger effects on more variables than richness. However, species-rich communities are likely to contain several species with differing effects on functions, which renders species richness important for functioning. Mixed meadows add to coastal ecosystem functioning in the northern Baltic Sea and may provide with services essential for human well-being.

Identification and application of bile metabolites to assess the exposure of fish to pharmaceuticals in the environment

Thousands of tons of pharmaceuticals are consumed yearly worldwide. Due to the continuous and increasing consumption and their incomplete elimination in wastewater treatment plants (WWTP), pharmaceuticals and their metabolites can be detected in receiving waters, although at low concentrations (ng to low μg/L). As bioactive molecules the presence of pharmaceuticals in the aquatic environment must be considered potentially hazardous for the aquatic organisms. In this thesis, the biotransformation and excretion of pharmaceuticals in fish was studied. The main biotransformation pathways of three anti‐inflammatory drugs, diclofenac, naproxen and ibuprofen, in rainbow trout were glucuronidation and taurine conjugation of the parent compounds and their phase I metabolites. The same metabolites were present in fish bile in aquatic exposures as in fish dosed with intraperitoneal injection. Higher bioconcentration factor in bile (BCFbile) was found for ibuprofen when compared to diclofenac and naproxen. Laboratory exposure studies were followed by a study of uptake of pharmaceuticals in a wild fish population living in lake contaminated with WWTP effluents. Of the analyzed 17 pharmaceuticals and six phase I metabolites, only diclofenac, naproxen and ibuprofen was present in bream and roach bile. It was shown, that diclofenac, naproxen and ibuprofen excreted by the liver can be found in rainbow trout and in two native fish species living in the receiving waters. In the bream and roach bile, the concentrations of diclofenac, naproxen and ibuprofen were roughly 1000 times higher than those found in the lake water, while in the laboratory exposures, the bioconcentration of the compounds and their metabolites in rainbow trout bile were at the same level as in wild fish or an order of magnitude higher. Thus, the parent compounds and their metabolites in fish bile can be used as a reliable biomarker to monitor the exposure of fish to environmental pharmaceuticals present in water receiving discharges from WWTPs.