Toxic potential of the emerging contaminant nicotine to the aquatic ecosystem

Nicotine is a “life-style compound” widely consumed by human populations and, consequently, often found in surface waters. This fact presents a concern for possible effects in the aquatic ecosystems. The objective of this study was to assess the potential lethal and sublethal toxicity of nicotine in aquatic organisms from different trophic levels (Vibrio fischeri, Pseudokirchneriella subcapitata, Thamnocephalus platyurus, and Daphnia magna). The bioassays were performed by exposing the organisms to concentrations of nicotine in a range of 0.5–1000 μg/L. Results showed that nicotine, at tested concentration, was not acutely toxic to V. fischeri and T. platyurus. On the contrary, this substance exhibited toxicity to P. subcapitata and Daphnia magna. Thus, concentrations of nicotine of 100 and 200 μg/L promoted an inhibition in the growth of P. subcapitata. In addition, a concentration of 100 μg/L nicotine acted on the reproduction of the crustacean D. magna, by decreasing the number of juveniles produced by female. On the other hand, the results showed that concentrations equal to or greater than 10 μg/L induced the production of daphnids male offspring, which may indicate that nicotine is a weak juvenoid compound of the D. magna endocrine system. Furthermore, the result showed that concentrations tested of this chemical have the capacity to revert the effect of fenoxycarb, a strong juvenoid chemical insecticide. The results of the study revealed that nicotine can induce several changes in some of the most important key groups of the aquatic compartment, which can compromise, in a short time, the balance of aquatic ecosystem. Finally, a preliminary environmental risk assessment of this stimulant was performed from the highest measured concentration in surface water and the no observable effect concentration value in the most sensitive species, i.e., D. magna. This process revealed that nicotine can produce an important risk to aquatic organisms.     

VOC composition of current motor vehicle fuels and vapors, and collinearity analyses for receptor modeling

The formulation of motor vehicle fuels can alter the magnitude and composition of evaporative and exhaust emissions occurring throughout the fuel cycle. Information regarding the volatile organic compound (VOC) composition of motor fuels other than gasoline is scarce, especially for bioethanol and biodiesel blends. This study examines the liquid and vapor (headspace) composition of four contemporary and commercially available fuels: gasoline (<10% ethanol), E85 (85% ethanol and 15% gasoline), ultra-low sulfur diesel (ULSD), and B20 (20% soy-biodiesel and 80% ULSD). The composition of gasoline and E85 in both neat fuel and headspace vapor was dominated by aromatics and n-heptane. Despite its low gasoline content, E85 vapor contained higher concentrations of several VOCs than those in gasoline vapor, likely due to adjustments in its formulation. Temperature changes produced greater changes in the partial pressures of 17 VOCs in E85 than in gasoline, and large shifts in the VOC composition. B20 and ULSD were dominated by C₉ to C₁₆n-alkanes and low levels of the aromatics, and the two fuels had similar headspace vapor composition and concentrations. While the headspace composition predicted using vapor-liquid equilibrium theory was closely correlated to measurements, E85 vapor concentrations were underpredicted. Based on variance decomposition analyses, gasoline and diesel fuels and their vapors VOC were distinct, but B20 and ULSD fuels and vapors were highly collinear. These results can be used to estimate fuel related emissions and exposures, particularly in receptor models that apportion emission sources, and the collinearity analysis suggests that gasoline- and diesel-related emissions can be distinguished.     

Toxicity of two types of silver nanoparticles to aquatic crustaceans Daphnia magna and Thamnocephalus platyurus

Although silver nanoparticles (NPs) are increasingly used in various consumer products and produced in industrial scale, information on harmful effects of nanosilver to environmentally relevant organisms is still scarce. This paper studies the adverse effects of silver NPs to two aquatic crustaceans, Daphnia magna and Thamnocephalus platyurus. For that, silver NPs were synthesized where Ag is covalently attached to poly(vinylpyrrolidone) (PVP). In parallel, the toxicity of collargol (protein-coated nanosilver) and AgNO₃ was analyzed. Both types of silver NPs were highly toxic to both crustaceans: the EC50 values in artificial freshwater were 15–17 ppb for D. magna and 20–27 ppb for T. platyurus. The natural water (five different waters with dissolved organic carbon from 5 to 35 mg C/L were studied) mitigated the toxic effect of studied silver compounds up to 8-fold compared with artificial freshwater. The toxicity of silver NPs in all test media was up to 10-fold lower than that of soluble silver salt, AgNO₃. The pattern of the toxic response of both crustacean species to the silver compounds was almost similar in artificial freshwater and in natural waters. The chronic 21-day toxicity of silver NPs to D. magna in natural water was at the part-per-billion level, and adult mortality was more sensitive toxicity test endpoint than the reproduction (the number of offspring per adult).     

Amendment application in a multi-contaminated mine soil: effects on soil enzymatic activities and ecotoxicological characteristics

Several amendments were tested on soils obtained from an arsenopyrite mine, further planted with Arrhenatherum elatius and Festuca curvifolia, in order to assess their ability to improve soil's ecotoxicological characteristics. The properties used to assess the effects were: soil enzymatic activities (dehydrogenase, β-glucosidase, acid phosphatase, urease, protease and cellulase), terrestrial bioassays (Eisenia fetida mortality and avoidance behaviour), and aquatic bioassays using a soil leachate (Daphnia magna immobilisation and Vibrio fischeri bioluminescence inhibition). The treatment with FeSO₄ 1 % w/w was able to reduce extractable As in soil, but increased the extractable Cu, Mn and Zn concentrations, as a consequence of the decrease in soil pH, in relation to the unamended soil, from 5.0 to 3.4, respectively. As a consequence, this treatment had a detrimental effect in some of the soil enzymatic activities (e.g. dehydrogenase, acid phosphatase, urease and cellulase), did not allow plant growth, induced E. fetida mortality in the highest concentration tested (100 % w/w), and its soil leachate was very toxic towards D. magna and V. fischeri. The combined application of FeSO₄ 1 % w/w with other treatments (e.g. CaCO₃ 1 % w/w and paper mill 1 % w/w) allowed a decrease in extractable As and metals, and a soil pH value closer to neutrality. As a consequence, dehydrogenase activity, plant growth and some of the bioassays identified those as better soil treatments to this type of multi-contaminated soil.     

A comparison of acute toxicity of biodiesel, biodiesel blends, and diesel on aquatic organisms

The increased demand of alternative energy sources has created interest in biodiesel and biodiesel blends; biodiesel is promoted as a diesel substitute that is safer, produces less harmful combustion emissions, and biodegrades more easily. Like diesel spills, biodiesel can have deleterious effects on the aquatic environments. The effect of neat biodiesel, biodiesel blends, and diesel on Oncorhynchus mykiss and Daphnia magna was evaluated using acute toxicity testing. Static nonrenewal bioassays of freshwater organisms containing B100, B50, B20, B5, and conventional diesel fuel were used to compare the acute effects of biodiesel to diesel. Mortality was the significant end point measured in this study; percent mortality and lethal concentration (LC50) at different exposure times were determined from the acute toxicity tests performed. Trials were considered valid if the controls exhibited > 90% survival. Based on percentage of mortality and LC50 values, a toxicity ranking of fuels was developed.     

Comparative acute freshwater hazard assessment and preliminary PNEC development for eight fluorinated acids

Short-term 48, 72 and 96-h aquatic toxicity tests were conducted to evaluate the acute toxicity of eight fluorinated acids to the cladoceran, Daphnia magna, the green alga, Pseudokirchneriella subcapitata, and the rainbow trout, Oncorhynchus mykiss or the fathead minnow, Pimephales promelas. The eight fluorinated acids studied were tridecafluorohexyl ethanoic acid (6:2 FTCA), heptadecafluorooctyl ethanoic acid (8:2 FTCA), 2H-dodecafluoro-2-octenoic acid (6:2 FTUCA), 2H-hexadecafluoro-2-decenoic acid (8:2 FTUCA), 2H,2H,3H,3H-undecafluoro octanoic acid (5:3 acid), 2H,2H,3H,3H-pentadecafluoro decanoic acid (7:3 acid), n-perfluoropentanoic acid (PFPeA) and n-perfluorodecanoic acid (PFDA). The results of the acute toxicity tests conducted during this study suggest that the polyfluorinated acids, 8:2 FTCA, 8:2 FTUCA, 6:2 FTCA, 6:2 FTUCA, 7:3 acid and 5:3 acid, and the perfluorinated acids PFPeA and PFDA, are generally of low to medium concern based on evaluation of their acute freshwater toxicity (EC/LC50s typically between 1 and >100 mg L⁻¹) using the USEPA TSCA aquatic toxicity evaluation paradigm. For the polyfluorinated acids, aquatic toxicity generally decreased as the number of fluorinated carbons decreased and as the overall carbon chain length decreased from 12 to 8. Acute aquatic toxicity of the 5 and 10 carbon perfluorocarboxylic acids (EC/LC50s between 10.6 and >100 mg L⁻¹) was greater or similar to that of the 6-9 carbon perfluorocarboxylic acids (EC/LC50s > 96.5 mg L⁻¹). This study also provides the first report of the acute aquatic toxicity of the 5:3 acid (EC/LC50s of 22.5 to >103 mg L⁻¹) which demonstrated less aquatic toxicity than the 7:3 acid (EC/LC50s of 0.4-32 mg L⁻¹). The cladoceran, D. magna and the green alga, P. subcapitata had generally similar EC50 values for a given substance while fish were typically equally or less sensitive with the exception that PFPeA was most toxic to fish. Predicted no-effect concentrations (PNECs) were estimated using approaches consistent with REACH guidance and when compared with available environmental concentrations, these PNECs suggest that the fluorinated acids tested pose little risk for aquatic organisms.     

Application of a battery of biotests for the determination of leachate toxicity to bacteria and invertebrates from sewage sludge-amended soil

The objective of the study was to determine the leachates toxicity from sewage sludge-amended soils (sandy and loamy). Samples originated from a plot experiment realized over a period of 29 months. Two types of soil were fertilized with sewage sludges at the dose of 3 % (90 t/ha). Soil samples were taken after 0, 7, 17, and 29 months from the application of sewage sludges. Leachates were obtained according to the EN 12457–2 protocol. The following commercial tests were applied for the estimation of the toxicity: Microtox (Vibrio fischeri), Microbial assay for toxic risk assessment (ten bacteria and one yeast), Protoxkit F? (Tetrahymena thermophila), Rotoxkit F? (Brachionus calyciflorus), and Daphtoxkit F? (Daphnia magna). The test organisms displayed varied toxicity with relation to the soils amended with sewage sludges. The toxicity of the leachates depended both on the soil type and on the kind of sewage sludge applied. Notable differences were also observed in the sensitivity of the test organisms to the presence of sewage sludge in the soil. The highest sensitivity was a characteristic of B. calyciflorus, while the lowest sensitivity to the presence of the sludges was revealed by the protozoa T. thermophila. Throughout the periods of the study, constant variations of toxicity were observed for most of the test organisms. The intensity as well as the range of those variations depended both on the kind of test organism and on the kind of sludge and soil type. In most cases, an increase of the toxicity of soils amended with the sewage sludges was observed after 29 months of the experiment.     

Toxicity identification evaluation of anaerobically treated swine slurry: A comparison between Daphnia magna and Raphanus sativus

Anaerobic digestion does not efficiently reduce ionic compounds present in swine slurry, which could present a potential risk to aquatic ecosystems (surface runoff) and terrestrial ambient (irrigation). The objective of this study was to evaluate the ecotoxicological characteristics of anaerobically treated swine slurry using acute and chronic (epicotyl elongation) toxicity tests with Daphnia magna and Raphanus sativus and identification of suspected toxic compounds using the Toxicity Identification Evaluation (TIE) method. The evaluation was performed in three phases: physicochemical characterization of the slurry; acute/chronic toxicity testing with Daphnia magna and Raphanus sativus for each fraction of the TIE (cation and anion exchange columns, activated carbon, pH modification/aeration and EDTA) and identification of suspected toxic compounds. The anaerobically treated slurry contained concentrations of ammonium of 1,072 mg L^?1, chloride of 815 mg L^?1 and metals below 1 mg L^?1 with a D. magna acute toxicity (48h-LC₅₀) of 5.3% and R. sativus acute toxicity (144h-LC₅₀) of 48.1%. Epicotyl elongation of R. sativus was inhibited at concentrations above 25% (NOEC). The cation exchange reduced the toxicity and free ammonia by more than 90% for both bio-indicators. Moreover, this condition stimulated the epicotyl growth of R. sativus between 10% and 37%. In conclusion, the main compound suspected of causing acute toxicity in D. magna and acute/chronic toxicity in R. sativus is the ammonium. The findings suggest the need the ammonium treatment prior to the agricultural reuse of swine slurry given the high risk to contaminate the aquatic environment by runoff and toxicity of sensitive plants.     

Efficiency of a cleanup technology to remove mercury from natural waters by means of rice husk biowaste: ecotoxicological and chemical approach

In the present work, the efficiency of rice husk to remove Hg(II) from river waters spiked with realistic environmental concentrations of this metal (μg L^?1 range) was evaluated. The residual levels of Hg(II) obtained after the remediation process were compared with the guideline values for effluents discharges and water for human consumption, and the ecotoxicological effects using organisms of different trophic levels were assessed. The rice husk sorbent proved to be useful in decreasing Hg(II) contamination in river waters, by reducing the levels of Hg(II) to values of ca. 8.0 and 34 μg L^?1, for an Hg(II) initial concentration of 50 and 500 μg L^?1, respectively. The remediation process with rice husk biowaste was extremely efficient in river waters spiked with lower levels of Hg(II), being able to eliminate the toxicity to the exposed organisms algae Pseudokirchneriella subcapitata and rotifer Brachionus calyciflorus and ensure the total survival of Daphnia magna species. For concentrations of Hg(II) tenfold higher (500 μg L^?1), the remediation process was not adequate in the detoxification process, still, the rice husk material was able to reduce considerably the toxicity to the bacteria Vibrio fischeri, algae P. subcapitata and rotifer B. calyciflorus, whose responses where fully inhibited during its exposure to the non-remediated river water. The use of a battery of bioassays with organisms from different trophic levels and whose sensitivity revealed to be different and dependent on the levels of Hg(II) contamination proved to be much more accurate in predicting the ecotoxicological hazard assessment of the detoxification process by means of rice husk biowaste.     

Photolysis of flumequine: identification of the major phototransformation products and toxicity measures

Direct photolysis of flumequine (FLU, 20 mg L⁻¹) in different types of water (demineralised water (DW) and synthetic seawater (SW)), was conducted in a Suntest CPS + solar simulator to evaluate its persistence and toxicity, and to identify the major phototransformation products (PTPs) generated during photolysis in DW. It was observed that FLU is susceptible to transformation when subjected to direct solar radiation. The composition of the water affects the FLU degradation kinetics, which is slower in SW. Photolytic transformation products generated during direct photolysis were identified by liquid chromatography-time of flight-mass spectrometry (LC-TOF-MS). Fourteen PTPs generated in DW were identified. The transformation of FLU begins with the opening of the heterocyclic ring by oxidation of the double bond. Loss of the fluorine atom and the hydroxylation of the aromatic ring also appear as the majority, especially in the early stages. Comparative acute toxicity evaluation by Vibrio fischeri and Daphnia magna bioassays was performed for the first and last irradiated solutions in both matrices studied. These bioassays demonstrated that in the SW matrix, the most persistent PTPs are highly toxic to D. magna but less so to V. fischeri.     

Environmental effects of soil contamination by shale fuel oils

Estonia is currently one of the leading producers of shale oils in the world. Increased production, transportation and use of shale oils entail risks of environmental contamination. This paper studies the behaviour of two shale fuel oils (SFOs)—‘VKG D’ and ‘VKG sweet’—in different soil matrices under natural climatic conditions. Dynamics of SFOs’ hydrocarbons (C10–C40), 16 PAHs, and a number of soil heterotrophic bacteria in oil-spiked soils was investigated during the long-term (1 year) outdoor experiment. In parallel, toxicity of aqueous leachates of oil-spiked soils to aquatic organisms (crustaceans Daphnia magna and Thamnocephalus platyurus and marine bacteria Vibrio fischeri) and terrestrial plants (Sinapis alba and Hordeum vulgare) was evaluated. Our data showed that in temperate climate conditions, the degradation of SFOs in the oil-contaminated soils was very slow: after 1 year of treatment, the decrease of total hydrocarbons’ content in the soil did not exceed 25 %. In spite of the comparable chemical composition of the two studied SFOs, the VKG sweet posed higher hazard to the environment than the heavier fraction (VKG D) due to its higher mobility in the soil as well as higher toxicity to aquatic and terrestrial species. Our study demonstrated that the correlation between chemical parameters (such as total hydrocarbons or total PAHs) widely used for the evaluation of the soil pollution levels and corresponding toxicity to aquatic and terrestrial organisms was weak.     

Acute toxicity of chlorpyrifos to embryo and larvae of banded gourami Trichogaster fasciata

This study elucidated the acute toxicity of chlorpyrifos on the early life stages of banded gourami (Trichogaster fasciata). To determine the acute effects of chlorpyrifos on their survival and development, we exposedthe embryos and two-day-old larvae to six concentrations (0, 0.01, 0.10, 1.0, 10 and 100 µg L^?1) of chlorpyrifos in plastic bowls. Log-logistic regression was used to calculate LC10 and LC50 values. Results showed that embryo mortality significantly increased with increasing chlorpyrifos concentrations. The 24-h LC10 and LC50 values (with 95% confidence limits) of chlorpyrifos for embryos were 0.89 (0.50–1.58) and 11.8 (9.12–15.4) µg L^?1, respectively. Hatching success decreased and mortality of larvae significantly increased with increasing concentrations of chlorpyrifos. The 24-h LC10 and LC50 values (with 95% confidence limits) of chlorpyrifos for larvae were 0.53 (0.27–1.06) and 21.7 (15.9–29.4) µg L^?1, respectively; the 48-h LC10 and LC50 for larvae were 0.04 (0.02–0.09) and 5.47 (3.77–7.94) µg L^?1, respectively. The results of this study suggest that 1 µg L^?1 of chlorpyrifos in the aquatic environment may adversely affect the development and the reproduction of banded gourami. Our study also suggests that banded gourami fish can serve as an ideal model species for evaluating developmental toxicity of environmental contaminants.     

Comparative toxicity of rac- and S-tebuconazole to Daphnia magna

Tebuconazole is a chiral triazole fungicide used as raceme in a variety of agricultural applications. Earlier studies showed that tebuconazole is toxic to many non-target aquatic organisms but relative data for tebuconazole enantiomers are lacking. Thus, goal of this study was to evaluate and compare the toxicity of rac- and S-tebuconazole with Daphnia magna at both acute and chronic levels according to Organization for Economic Cooperation and Development (OECD) guidelines 202 and 211 respectively, to provide some guidelines for optimizing chiral pesticides application and management. The exposure concentrations were 0.1, 0.5, 1, 2, 4, 8, 10 mg L^?1 for both rac- and S-tebuconazole and their 48-h EC₅₀ values to D. magna were 3.53 (3.32–3.78) and 2.74 (2.33–3.10) mg L^?1 respectively, indicating that these both are medium toxic to D. magna with no significant toxicity difference at acute level. In chronic test, <24-h old D. magna were exposed to 0.01, 0.05, 0.10, 0.20, and 0.40 mg L^?1 of rac- and S-tebuconazole with one blank and one solvent control for 21 days according to OECD guideline 211. Four developmental (molting rate, days to the 1st and 3rd brood, and body length) and five reproductive (size of the 1st and 3rd brood, number of broods, and number of neonates) parameters for each D. magna were determined. Results showed that both rac- and S-tebuconazole significantly reduced the reproduction and impacted the development of D. magna at concentrations of 0.05 mg L^?1 or higher. Furthermore, S-tebuconazole was more toxic than raceme, and the difference between effects on the same parameters induced by rac- and S-tebuconazole was statistically significant. These results demonstrated that the chronic toxicity of S-tebuconazole might be underestimated in general use, and further studies should focus more on the biological behaviors of enantiomers and not just the raceme of tebuconazole and other chiral pesticides in the environment.     

Gasoline Evaporation–Ethanol and Nonethanol Blends

Tests were performed to compare the evaporation rate of 10 volume percent (vol%) ethanol-blended gasoline (E10) with the evaporation rate of its base gasoline. Weight loss, temperature, pressure, and humidity were monitored as lab-blended E10 and base gasolines were evaporated concurrently from glass cylinders placed on balances located side by side under an exhaust hood. The averaged results of four tests at about 70°F showed that the E10 lost more total weight to evaporation than the base fuel, but less gasoline. The increased weight was due to ethanol, which was present in the E10 evaporative emissions at concentrations of about 13 weight percent (wt%). In two-hour tests at temperatures near 70°F, during which 4.5 to 5.3 wt% of initial fuel samples were evaporated, E10 fuels lost an average of about 5% less gasoline than their base fuels. A similar result was obtained for a one-hour test, during which about 2.4 to 2.5 wt% of the initial fuel samples were evaporated. Gas chromatography (GC) component analysis indicated that the compositions of the ethanol-free emissions from the two fuels were similar. Reid vapor pressure (RVP) measurements made using a Grabner CCA-VPS according to ASTM D5191-91 indicated that E10 fuels underwent an approximate 5% greater RVP reduction than their respective base fuels.     

Aquatic ecotoxicity assessment of a new natural formicide

Background, aim and scope

Agrochemicals could reach aquatic ecosystems and damage ecosystem functionality. Natural formicide could be an alternative to use in comparison with the more toxic formicides available on the market. Thus, the objective of this study was to assess the ecotoxicity of the new natural formicide Macex? with a battery of classical aquatic ecotoxicity tests.

Material and methods

Bacteria (Aliivibrio fischeri), algae (Pseudokirchneriella subcapitata), hydra (Hydra attenuata), daphnids (Daphnia magna), and fish (Danio rerio) tests were performed in accordance with international standardized methodologies.

Results

In the range of formicide concentrations tested (0.03 to 2.0?g?L^?1) EC₅₀ values varied from 0.49 to >2.0?g?L^?1, with P. subcapitata being the most sensitive species and H. attenuata and D. rerio the most tolerant species to this product in aqueous solutions.

Conclusions

This new formicide preparation can be classed as a product of low toxicity compared to the aquatic ecotoxicity of the most common commercialized formicides.     

Partitioning of aromatic and oxygenated constituents into water from regular and ethanol-blended gasolines

Variability in gasoline-water partitioning of major aromatic constituents (benzene, toluene, ethylbenzene, and xylenes (BTEX)) and methyl tert-butyl ether (MTBE) were examined for regular and ethanol-blended gasolines. By use of a two-phase liquid-liquid equilibrium model, the distribution of nonpolar solutes between fuel phase and water was related to principles of equilibrium. The models derived using Raoult's law convention for activity coefficients and liquid solubility is presented. The observed inverse log-log linear dependence of K_fw values on aqueous solubility, could be well predicted by assuming gasoline to be an ideal solvent mixture. Oxygenated additives (i.e., ethanol and MTBE), in the low percent range (below 5%), were shown to have minimal or negligible cosolvent effects on hydrocarbon partitioning. In the case of high fuel-to-water ratio (e.g., 1:1) or near contaminant source zone, the cosolvent effect of oxygenated gasoline with high content of ethanol (e.g., E85) will be environmentally significant.     

Chemical and ecotoxicological analyses of sediments and elutriates of contaminated rivers due to e-waste recycling activities using a diverse battery of bioassays

A multi-trophic, multi-exposure phase assessment approach was applied to characterize the toxicity of sediments collected from two rivers in Guiyu, China, an e-waste recycling centre. Elutriate toxicity tests (bacterium Vibrio fischeri and microalga Selenastrum capricornutum) and whole sediment toxicity test (crustacean Heterocypris incongruens) showed that most sediments exhibited acute toxicity, due to elevated heavy metals and PAHs levels, and low pH caused by uncontrolled acid discharge. The survival rates of crustaceans were negatively (p < 0.05) correlated with total PAHs in sediments (411-1755 mg kg⁻¹); EC50s of V. fischeri on the elutriates were significantly correlated with elutriate pH (p < 0.01). Significant (p < 0.05) correlations between the induction of hepatic metallothionein in tilapia (Oreochromis mossambicus) and metal concentrations (Cu, Zn, Pb) in sediments were also observed, when fish were fed with diets containing sediment. The results showed that uncontrolled e-waste recycling activities may bring adverse effects to local aquatic ecosystem.     

Electrochemical mineralization and detoxification of naphthenic acids on boron-doped diamond anodes

Electrochemical oxidation (ELOX) with boron-doped diamond (BDD) anodes was successfully applied to degrade a model aqueous solution of a mixture of commercial naphthenic acids (NAs). The model mixture was prepared resembling the NA and salt composition of oil sands process-affected water (OSPW) as described in the literature. The initial concentration of NAs between 70 and 120 mg/L did not influence the electrooxidation kinetics. However, increasing the applied current density from 20 to 100 A/m² and the initial chloride concentration from 15 to 70 and 150 mg/L accelerated the rate of NA degradation. At higher chloride concentration, the formation of indirect oxidative species could contribute to the faster oxidation of NAs. Complete chemical oxygen demand removal at an initial NA concentration of 120 mg/L, 70 mg/L of chloride and applied 50 A/m² of current density was achieved, and 85% mineralization, defined as the decrease of the total organic carbon (TOC) content, was attained. Moreover, after 6 h of treatment and independently on the experimental conditions, the formation of more toxic species, i.e. perchlorate and organochlorinated compounds, was not detected. Finally, the use of ELOX with BDD anodes produced a 7 to 11-fold reduction of toxicity (IC₅₀ towards Vibrio fischeri) after 2 h of treatment.     

Biochemical biomarkers in Nile tilapia (Oreochromis niloticus) after short-term exposure to diesel oil, pure biodiesel and biodiesel blends

Fossil fuels such as diesel are being gradually replaced by biodiesel, a renewable energy source, cheaper and less polluting. However, little is known about the toxic effects of this new energy source on aquatic organisms. Thus, we evaluated biochemical biomarkers related to oxidative stress in Nile tilapia (Oreochromis niloticus) after two and seven exposure days to diesel and pure biodiesel (B100) and blends B5 and B20 at concentrations of 0.01 and 0.1 mL L⁻¹. The hepatic ethoxyresorufin-O-deethylase activity was highly induced in all groups, except for those animals exposed to B100. There was an increase in lipid peroxidation in liver and gills in the group exposed to the higher concentration of B5. All treatments caused a significant increase in the levels of 1-hydroxypyrene excreted in the bile after 2 and 7 d, except for those fish exposed to B100. The hepatic glutathione-S-transferase increased after 7 d in animals exposed to the higher concentration of diesel and in the gill of fish exposed to the higher concentration of pure diesel and B5, but decreased for the two tested concentrations of B100. Superoxide dismutase, catalase and glutathione peroxidase also presented significant changes according to the treatments for all groups, including B100. Biodiesel B20 in the conditions tested had fewer adverse effects than diesel and B5 for the Nile tilapia, and can be suggested as a less harmful fuel in substitution to diesel. However, even B100 could activate biochemical responses in fish, at the experimental conditions tested, indicating that this fuel can also represent a risk to the aquatic biota.     

Ecotoxicity and fungal deterioration of recycled polypropylene/wood composites: Effect of wood content and coupling

Recycled polypropylene (rPP) was recovered from an industrial shredder and composites were prepared with a relatively wide range of wood content and with two coupling agents, a maleated PP (MAPP) and a maleated ethylene-propylene-diene elastomer (MAEPDM). The mechanical properties of the composites showed that the coupling agents change structure only slightly, but interfacial adhesion quite drastically. The durability of the materials was determined by exposing them to a range of fungi and, ecotoxicity was studied on the aquatic organism Vibrio fischeri. The composites generally exhibit low acute toxicity, with values below the levels considered to have direct ecotoxic effect on aquatic ecosystems (<2 toxic units). Their toxicity to V. fischeri depended on the presence of the coupling agents with larger E₅₀ values in 24-h aqueous extracts from composites containing MAPP or MAEPDM in comparison to composites without any coupling agent. Evaluation of resistance against fungal colonization and deterioration proved that wood facilitates fungal colonization. Fungi caused slight mass loss (below 3%) but it was not correlated with substantial deterioration in material properties. MAPP seems to be beneficial in the retention of mechanical properties during fungal attack. rPP/wood composites can be considered non-ecotoxic and quite durable, but the influence of wood content on resistance to fungal attack must be taken into account for materials intended for applications requiring long-term outdoor exposure.