Bioremediation process on Brazil shoreline

GOAL, SCOPE AND BACKGROUND: Bioremediation technique can be considered a promising alternative to clean oil spills using microbial processes to reduce the concentration and/or the toxicity of pollutants. To understand the importance of this work we must know that there is only little research performed to date using bioremediation techniques to clean oil spills in tropical countries. So, the main objective of this work is to analyze the behavior of a laboratory's bioremediation test using nutrients on coastal sediments. METHODS: The bioremediation process is followed through geochemical analysis during the tests. This organic material is analyzed by medium pressure liquid chromatography (MPLC), gas chromatography/flame ionization detection (GC/FID) and gas chromatography/ mass spectrometry. By microbial counting, the number of total bacteria and degrading bacteria is determined during the experiments, in order to confirm the effectiveness of the bioremediation process. The seawater obtained throughout the bioremediation process is analyzed for nutrients grade (phosphate and ammonium ions) and also for its toxicity (Microtox tests) due the presence of hydrocarbons and fertilizer. RESULTS: The results from the geochemical analyses of the oil show a relative decrease in the saturated hydrocarbon fraction that is compensated by a relative enrichment on polar compounds. It's confirmed by the fingerprint evaluation where it is possible to see a complete reduction of the normal alkanes followed by isoprenoids. Seawater analysis done by toxicity and nutrients analysis, such as microbial counting (total and degrading bacteria), confirm the fertilizer effectiveness during the bioremediation process. DISCUSSION: Results from simulating test using NPK, a low-price plant fertilizer, suggest that it's able to stimulate the degradation process. Results from medium pressure liquid chromatography (MPLC), done at two different depths (surface and subsurface), show different behavior during the biodegradation process where the later is seen to be more susceptible to microbial attack. Data from bioremediation unit shows a bigger reduction of the saturated fraction, followed by some smaller reduction of aromatic fractions, compensated by a relative increase from polar compounds (NSO). n-C17/pristane, n-C18/ fitane and pristane/fitane rates show constant values for the unity control, different from bioremediation samples which have a significant reduction, especially on subsurface areas, where a strong fall in the rates, seen to be reduced to zero over twenty days, had occurred during the first ten days. However, sample surfaces are reduced to zero in thirty days of experiments, proving that biodegradation is better on subsurfaces. Gaseous chromatography/mass spectrometry (CG/MS) analysis shows constant values to cyclic biomarker rates and aromatic compounds, suggesting that the biodegradation process is not strong enough to reduce these composites. Microbial analysis shows a reduction on heterotrophic (total bacteria) number from control unit, probably because the bacteria uses the spill oil like carbon source and energy. However, the number increases on bioremediation unit, because it uses NPK like a biostimulator. The hydrocarbonoclastic number isn't enough on the first moment, but it's detected after 30 days and quantified in all units, showing big values especially in bioremediation. Toxicity tests confirm that NPK fertilizer does not intoxicate the shoreline during the application of the bioremediation technique. Some nutrient concentration shows high values of ammonium and phosphate per bioremediation unit, reducing by the end of the experiment. CONCLUSIONS: Results reached the goal, finding a proper nutrient (NPK fertilizer) to stimulate the biodegradation process, growing bacteria responsible for reducing impact-contaminated coast ambient by oil spills. Chemical analysis of oil shows a reduction in the saturated fraction with a relative enrichment in polar composites (NSO) and the aromatic fraction from oil remaining constant. Subsurface samples show more biodegradation than surface samples, probably because the first one has higher humidity. Linear alcanes are more biodegraded than isoprenoids, confirming the biodegradation susceptibility order. Saturated cyclic biomarkers and aromatic compounds show constant behavior maybe because the nutrients or time was not enough for microorganismic attack. Fertilizer does not demonstrate any toxic effects in local biota so that it does not compromise the technique applicability and the environment is not saturated by nutrients during the simulation, especially since the coastal environment is an open system affected daily by tides. Therefore, bioremediation tests can be classified as moderate, reaching level 5 in the classification scale by Peters & Moldowan (1993). RECOMMENDATIONS AND PERSPECTIVES: The use of marine environment by the petroleum industry on exploration, production and transportation operation, transform this oil to become the most important pollutant in the oceans. Bioremediation is an important technique used to clean spilled oil impacting on shorelines, accelerating the biodegradation process by using fertilizer growing the microorganisms responsible for decontaminating the environment. We recommend confirming the efficiency of NPK nutrient used on bioremediation simulating experiments on beaches, while monitoring the chemical changes long-term. NPK fertilizer can be used to stimulate the biodegradation process on shoreline impacted by spilled oil.     

Source apportionment of fine particles in Tennessee using a source-oriented model

Source apportionment of fine particles (PM2.5, particulate matter < 2 microm in aerodynamic diameter) is important to identify the source categories that are responsible for the concentrations observed at a particular receptor. Although receptor models have been used to do source apportionment, they do not fully take into account the chemical reactions (including photochemical reactions) involved in the formation of secondary fine particles. Secondary fine particles are formed from photochemical and other reactions involving precursor gases, such as sulfur dioxide, oxides of nitrogen, ammonia, and volatile organic compounds. This paper presents the results of modeling work aimed at developing a source apportionment of primary and secondary PM2.5. On-road mobile source and point source inventories for the state of Tennessee were estimated and compiled. The national emissions inventory for the year 1999 was used for the other states. U.S. Environmental Protection Agency Models3/Community Multi-Scale Air Quality modeling system was used for the photochemical/secondary particulate matter modeling. The modeling domain consisted of a nested 36-12-4-km domain. The 4-km domain covered the entire state of Tennessee. The episode chosen for the modeling runs was August 29 to September 9, 1999. This paper presents the approach used and the results from the modeling and attempts to quantify the contribution of major source categories, such as the on-road mobile sources (including the fugitive dust component) and coal-fired power plants, to observed PM2.5 concentrations in Tennessee. The results of this work will be helpful in policy issues targeted at designing control strategies to meet the PM2.5 National Ambient Air Quality Standards in Tennessee.     

Analysis of the nitrifying bacterial community in BioCube sponge media using fluorescent in situ hybridization (FISH) and microelectrodes

There is growing interest in the development of more cost-effective and retrofit technologies for the upgrade and expansion of existing wastewater treatment plants with extreme space constraints. A free-floating sponge media (BioCube) process, using a 24L lab scale reactor, was operated to study the nitrification profiles and microbial community. The COD removal efficiencies were maintained, at an average of 95%, with the mixed liquor suspended solids (MLSS) inside the BioCube sponge media maintained at 12,688mg/L. The nitrification removal efficiencies were between 92% and 100%, with an average value of 99%. From the results of microelectrode measurements, the ammonium ion concentration was found to rapidly decrease from the surface of the BioCube sponge media to a depth of 2mm due to chemical reactions carried out by ammonia oxidizing bacteria (AOB) species. Multi-fluorescence in situ hybridization (FISH) has been used to investigate the spatial distributions of various microbial activities within reactors. Microbial communities were targeted using different oligonucleotide probes specific to AOB and nitrite oxidizing bacteria (NOB). There were a large number of AOB populations, but these were not uniformly distributed in the biofilm compared to the NOB populations.     

Measuring bed shear stress along vegetated river beds using FST-hemispheres

The measurement of the bed shear stress along vegetated river beds is essential for accurately predicting the water level, velocity and solute and sediment transport fluxes in computational hydroenvironmental models. Details are given herein of an experimental and theoretical study to determine the bed boundary shear stress along vegetated river beds introducing a novel field measuring method, namely the FliessWasserStammtisch (FST)-hemispheres. Although investigations have been conducted previously for sedimentary channels using the FST-hemispheres, this preliminary study is thought to be the first time that such hemispheres have been used to investigate the bed shear stresses in vegetated channels. FST-hemispheres were first developed by Statzner and Müller [1989. Standard hemispheres as indicators of flow characteristics in lotic benthos research. Freshwater Biology 21, 445-459] to act as an integrated indicator of the gross hydrodynamic stresses present near the bed. Test and validation data were found to be at least of the same order of magnitude for the stresses predicted from literature for sedimentary channels, with this study establishing the commencement of a database of calibrated FST-hemisphere laboratory data for vegetated channel beds. In a series of experiments, depths ranging from 0.1 to 0.28m were considered, equating directly to comparable conditions in small rivers or streams. The results of this study provide a basis for enabling the FST-hemispheres to be used to evaluate the boundary shear stress for a wider range of applications in the future, including vegetated river beds.     

Ions species size distribution in particulate matter associated with VOCs and meteorological conditions over an urban region

Airborne particulate matter (PM10, PM2.5, PM1) and volatile organic compounds (benzene, toluene, m,p-xylene, o-xylene) samples were collected during winter and summer seasons of 2005 at two sites, representing an urban and a suburban region of the Greater Athens Area. Urban site traffic emissions were the major contributor to the concentration of PM2.5, PM10, toluene, and xylenes, while benzene and PM1 concentrations were presented in significant spatial variations. K+, Na+, Mg2+, Ca2+, NO3-, Cl- and SO42- ions were analyzed for the chemical characterization of the collected PM samples. The results showed that Na+ cations and SO42- anions were the dominant species, during winter and summer, respectively, in both sites. The analysis of the synoptic scale and mesoscale atmospheric circulation during the experimental periods demonstrated that the meteorological conditions play a key role, not only in the variation but also in the distribution of the ionic concentrations at the three fractions of particulates and the dominant character (alkaline/acidic/neutral) of the particulates at the two sampling sites.     

Assessment of chemical, biochemical and ecotoxicological aspects in a mine soil amended with sludge of either urban or industrial origin

A greenhouse pot experiment was conducted to evaluate the effect of sewage sludge (SS), of sugar beet sludge (SBS), or of a combination of both, in the remediation of a highly acidic (pH 3.6) metal-contaminated soil, affected by mining activities. The SS was applied at 100 and 200 Mg ha(-1) (dry weight basis), and the SBS at 7 Mg ha(-1). All pots were sown with Italian ryegrass (Lolium multiflorum Lam.). After 60 d of growth, shoot biomass was quantified and analysed for Cu, Pb and Zn. The pseudo-total and bioavailable contents of Cu, Pb and Zn and the enzymatic activities of beta-glucosidase, acid phosphatase, cellulase, protease and urease were determined in the soil mixtures. Two indirect acute bioassays with leachates from the soil (luminescent inhibition of Vibrio fischeri and Daphnia magna immobilization) were also used. The SS, in particular when in combination with SBS, corrected soil acidity, while increasing the total organic matter content and the cation exchange capacity. The application of SS led to a decrease in the level of effective bioavailable metals (extracted by 0.01 M CaCl(2), pH 5.7, without buffer), but caused an increase in their potential bioavailability (extracted by a solution of 0.5M NH(4)CH(3)COO, 0.5 M CH(3)COOH and 0.01 M EDTA, pH 4.7). Plant biomass increased more than 10 times in the presence of 100 Mg SS ha(-1), and more than five times with the combined use of 100 Mg SS ha(-1) and SBS, but a considerable phytotoxic effect was observed for the application rate of 200 Mg SS ha(-1). Copper, Pb and Zn concentrations in the shoots of L. multiflorum decreased significantly when using 100 Mg SS ha(-1) or SBS. The activities of beta-glucosidase, urease and protease increased with increasing SS applications rates, but cellulase had a reduced activity when using 200 Mg ha(-1)SS. Both amendments were able to suppress soil toxicity to levels that did not affect D. magna, but increased the soil leachate toxicity towards V. fischeri, especially with the application of 200 Mg SS ha(-1). This study showed that for this type of mine soils, and when using SS of similar composition, the maximum SS application rate should be 100 Mg ha(-1), and that liming the SS amended soil with SBS did not contribute to a further improvement in soil quality.     

Effect of decabromodiphenyl ether and antimony trioxide on controlled pyrolysis of high-impact polystyrene mixed with polyolefins

The controlled pyrolysis of polyethylene/polypropylene/polystyrene mixed with brominated high-impact polystyrene containing decabromodiphenyl ether as a brominated flame-retardant with antimony trioxide as a synergist was performed. The effect of decabromodiphenyl ether and antimony trioxide on the formation of its congeners and their effect on distribution of pyrolysis products were investigated. The controlled pyrolysis significantly affected the decomposition behavior and the formation of products. Analysis with gas chromatograph with electron capture detector confirmed that the bromine content was rich in step 1 (oil 1) liquid products leaving less bromine content in the step 2 (oil 2) liquid products. In the presence of antimony containing samples, the major portion of bromine was observed in the form of antimony bromide and no flame-retardant species were found in oil 1. In the presence of synergist, the step 1 and step 2 oils contain both light and heavy compounds. In the absence of synergist, the heavy compounds in step 1 oil and light compounds in step 2 oils were observed. The presence of antimony bromide was confirmed in the step 1 oils but not in step 2 oils.     

The effect of nitroaromatics' composition on their toxicity in vivo: novel, efficient non-additive 1D QSAR analysis

Novel 1D QSAR approach that allows analysis of non-additive effects of molecular fragments on toxicity has been proposed. Twenty-eight nitroaromatic compounds including some well-known explosives have been chosen for this study. The 50% lethal dose concentration for rats (LD50) was used as the estimation of toxicity in vivo to develop 1D QSAR models on the framework of Simplex representation of molecular structure. The results of 1D QSAR analysis show that even the information about the composition of molecules provides the main trends of toxicity changes. The necessity of consideration of substituents' mutual impacts for the development of adequate QSAR models of nitroaromatics' toxicity was demonstrated. Statistic characteristics for all the developed partial least squares QSAR models, except the additive ones are quite satisfactory (R2=0.81-0.92; Q2=0.64-0.83; R2 test=0.84-0.87). A successful performance of such models is due to their non-additivity i.e. possibility of taking into account the mutual influence of substituents in benzene ring which plays the governing role for toxicity change and could be mediated through the different C-H fragments of the ring. The correspondence between observed and predicted by these models toxicity values is good. This allowing combine advantages of such approaches and develop adequate consensus model that can be used as a toxicity virtual screening tool.     

Genotoxicity assessment of acute exposure of chlorpyrifos to freshwater fish Channa punctatus (Bloch) using micronucleus assay and alkaline single-cell gel electrophoresis

Chlorpyrifos (O,O-diethyl O-3,5,6-trichloro-2-pyridylphosphorothioate) is one of the organophosphate pesticides widely used in agricultural practices throughout world and irreversible inhibitor of cholinesterase in all animal species. Limited efforts have been made to study acute genotoxic effects of chlorpyrifos (CPF) in different tissues of fish using genotoxic biomarkers. Therefore, the present investigation was aimed to study the induction of DNA damage by CPF in freshwater teleost fish Channapunctatus using micronucleus assay (MN assay) and alkaline single-cell gel electrophoresis (comet assay). The value of LC(50) - 96 h of CPF was determined as 811.98 microgl(-1) for C. punctatus, in a semi-static system and on the basis of LC(50) value three acute concentrations viz., 203, 406 and 609 microgl(-1) were determined. The fishes were exposed to the different concentrations of CPF for 96 h and samplings were done at regular intervals for assessment of the MN frequencies and DNA damage. In general, significant effects (P<0.01) from both concentrations and time of exposure were observed in exposed fishes. It was found that the micronucleus induction was highest on 96 h at all concentrations in the peripheral blood. Similar trend was observed for the DNA damage measured in terms of the percentage of tail DNA in the lymphocyte and gill cells. This study explored the combined use of micronucleus assay and comet assay for in vivo laboratory studies using fresh water fish for screening the genotoxic potential of xenobiotics.