Pilot installation for the thermo-chemical characterisation of solid wastes

The increasing production and the large variety of wastes require operators of thermal treatment units to continuously adapt the installations or the functioning parameters to the different physical and chemical properties of the wastes. Usually, the treated waste is encountered in the form of heterogeneous mixtures. The classical tests such as thermogravimetry and calorimetric bomb operate component by component, separately. In addition to this, they can analyse only small quantities of waste at a time (a few grams). These common tests are necessary but insufficient in the global waste analysis in the view further thermal treatment. This paper presents an experimental installation, which was designed and built at the CNRS Science Division, Department of Industrial Methods, Compiègne University of Technology, France. It allows the determination of waste thermal and chemical properties by means of thermal treatment. Also, it is capable of continuously analysing significant quantities of waste (up to 50kg/h) as compared to the classical tests and it can work under various conditions: The installation reproduces the process conditions from incinerators or pyrolysis reactors. It also provides complete information on the kinetics of the waste thermal degradation and on the pollutant emissions. Using different mixtures of components present in the municipal solid waste and also in the reconstituted MSW samples, we defined a series of criteria for characterising waste behaviour during the stages of the main treatment process such as: feeding, devolatilisation/oxidation, advancement, solid residue evacuation, and pollutants emission.     

Leachate recirculation effects on waste degradation: study on columns

The purpose of this study is to determine the impact of leachate recirculation on the degradation of municipal solid wastes (bioreactor concept). The study was carried out using columns containing approximately 50 kg of waste, in order to follow waste degradation over a limited time. Three types of waste were studied: fresh waste of standard composition, fresh waste of fermentable composition and some 8-yr-old waste extracted from a site in France. Measurement of the global parameters, such as chemical oxygen demand (COD), volatile acidity, alkalinity, leachate conductivity, methane potential of the wastes and biogas production monitoring (volume of CO2 and CH4 produced), were carried out. The quantity of oxydizable matter and biogas production was increased by the leachate recirculation, and the duration of the first degradation phases was reduced in all cases. Chloride, ammonium and organic pollution accumulation was observed according to the duration of recirculation. After 400 days of degradation, waste stabilization seemed to be reached for all of the recirculated columns (COD<300 mg/L O2, and methane potential reached).     

Effects of sewage sludge blending on the coal combustion: a thermogravimetric assessment

Combustion of urban sewage sludge together with coal in existing infrastructures may be a sustainable management option energetically interesting for these materials, usually considered wastes. Thermogravimetric analysis was used to study the combustion of a semianthracite coal and the modifications undergone when adding a small percentage (2%, 5%, 10%) of sewage sludge. Both Differential Scanning Calorimetric analysis and Differential Thermogravimetry burning profiles showed differences between coal and sewage sludge combustion. However, the effects of adding a percentage of sewage sludge equal or smaller than 10% was hardly noticeable in terms of heat release and weight loss during the coal combustion. This was further proved by non-isothermal kinetic analysis, which was used to evaluate the Arrhenius activation energy corresponding to the co-combustion of the blends. This work shows that thermogravimetric analysis may be used as an easy rapid tool to asses the co-combustion of sewage sludge together with coal.     

Managing scuba divers to meet ecological goals for coral reef conservation

Marine protected areas increasingly are challenged to maintain or increase tourism benefits while adequately protecting resources. Although carrying capacity strategies can be used to cope with use-related impacts, there is little understanding of divers themselves, their management preferences, and how preferences relate to conservation goals. By using a stated preference choice modeling approach, we investigated the choices divers make in selecting diving trips to marine protected areas as defined by use level, access, level of supervision, fees, conservation education, and diving expectations. Logit models showed that divers preferred a more restrictive management scenario over the status quo. Divers favored reductions in the level of site use and increased levels of conservation education. Divers did not favor fees to access protected areas, having less access to the resource, or extensive supervision. Finally, divers were much more willing to accept increasingly restrictive management scenarios when they could expect to see increased marine life.     

Modified Fenton reaction for trichlorophenol dechlorination by enzymatically generated H2O2 and gluconic acid chelate

Glucose oxidase is a well-known enzyme that catalyzes the oxidation of β-d-glucose to produce gluconic acid and hydrogen peroxide. Fenton reaction is a powerful oxidation technology used for the oxidation of groundwater pollutants. For the application of Fenton reaction in groundwater remediation, successful operation of Fenton reaction near neutral pH, and on-site generation of both H₂O₂ and chelate will be beneficial. The focus of this experimental study was to couple the glucose oxidation reaction with chelate-based Fenton reaction. The idea was to use the hydrogen peroxide and chelate gluconic acid generated during glucose oxidation for the dechlorination of 2,4,6-trichlorophenol (TCP) by Fenton reaction. The oxidation of glucose was achieved using the enzyme in free and immobilized forms. The rate of production of hydrogen peroxide was determined for each system, and was used to estimate the time required for complete consumption of glucose during the process, thus avoiding any traces of glucose in the Fenton reaction. In the case of free enzyme reaction, separation of the enzyme was achieved using an ultrafiltration membrane before initiating the Fenton reaction. The oxidation of TCP by Fenton reaction was performed at varying ratios of gluconic acid/Fe, and its effect on the decomposition of TCP and H₂O₂ was studied. TCP degradation was studied both in terms of parent compound degradation and free chloride generation.     

Adsorption of natural organic matter from waters by iron coated pumice

Natural pumice particles were used as granular support media and coated with iron oxides to investigate their adsorptive natural organic matter (NOM) removal from waters. The impacts of natural pumice source, particle size fraction, pumice dose, pumice surface chemistry and specific surface area, and NOM source on the ultimate extent and rate of NOM removal were studied. All adsorption isotherm experiments were conducted employing the variable-dose completely mixed batch reactor bottle-point method. Iron oxide coating overwhelmed the surface electrical properties of the underlying pumice particles. Surface areas as high as 20.6m(2)g(-1) were achieved after iron coating of pumice samples, which are above than those of iron coated sand samples reported in the literature. For all particle size fractions, iron coating of natural pumices significantly increased their NOM uptakes both on an adsorbent mass- and surface area-basis. The smallest size fractions (<63 microm) of coated pumices generally exhibited the highest NOM uptakes. A strong linear correlation between the iron contents of coated pumices and their Freundlich affinity parameters (K(F)) indicated that the enhanced NOM uptake is due to iron oxides bound on pumice surfaces. Iron oxide coated pumice surfaces preferentially removed high UV-absorbing fractions of NOM, with UV absorbance reductions up to 90%. Control experiments indicated that iron oxide species bound on pumice surfaces are stable, and potential iron release to the solution is not a concern at pH values of typical natural waters. Based on high NOM adsorption capacities, iron oxide coated pumice may be a promising novel adsorbent in removing NOM from waters. Furthermore, due to preferential removal of high UV-absorbing NOM fractions, iron oxide coated pumice may also be effective in controlling the formation of disinfection by-products in drinking water treatment.     

Seasonal variations of selected herbicides and related metabolites in water, sediment, seaweed and clams in the Sacca di Goro coastal lagoon (Northern Adriatic)

This study assesses the status of Sacca di Goro coastal lagoon (Northern Adriatic, Italy) with respect to watershed pollution. Because 80% of its watershed is devoted to agriculture, plant protection products and their metabolites were found in the water column, sediments (the upper 0-15 cm layer), macroalgae (Ulva rigida) and clams (Tapes philippinarum). Five seasonal sampling campaigns were performed from May 2004 to April 2005 and concentrations measured in five stations in the lagoon and six in the watershed. Relatively high concentrations of the s-triazine - terbuthylazine -, urea herbicides - diuron - and alachlor were detected through the year mainly at stations directly influenced by the Po di Volano inflow. The concentrations of products in use follow a clear seasonal pattern with spring peaks. This pattern is also visible in the sediments as well as in biota. Among metabolites, hydroxylated compounds prevailed, often with concentrations greater than those of the parent compounds. For the most part of the year, the concentrations in biota were close to detection limits, with concentration peaks in spring.     

How Plants Cope with Foreign Compounds. Translocation of xenobiotic glutathione conjugates in roots of barley (Hordeum vulgare) (9 pp)

Background, Aim and Scope Numerous herbicides and xenobiotic organic pollutants are detoxified in plants to glutathione conjugates. Following this enzyme catalyzed reaction, xenobiotic GS-conjugates are thought to be compartmentalized in the vacuole of plant cells. In the present study, evidence is presented for long range transport of these conjugates in plants, rather than storage in the vacuole. To our knowledge this is the first report about the unidirectional long range transport of xenobiotic conjugates in plants and the exudation of a glutathione conjugate from the root tips. This could mean that plants possess an excretion system for unwanted compounds which give them similar advantages as animals. Materials and Methods: Barley plants (Hordeum vulgare L. cv. Cherie) were grown in Petri dishes soaked with tap water in the greenhouse. - Fluorescence Microscopy. Monobromo- and Monochlorobimane, two model xenobiotics that are conjugated rapidly in plant cells with glutathione, hereby forming fluorescent metabolites, were used as markers for our experiments. Their transport in the root could be followed sensitively with very good temporal and spatial resolution. Roots of barley seedlings were cut under water and the end at which xenobiotics were applied was fixed in an aperture with a thin latex foil and transferred into a drop of water on a cover slide. The cover slide was fixed in a measuring chamber on the stage of an inverse fluorescence microscope (Zeiss Axiovert 100). - Spectrometric enzyme assay. Glutathione S-transferase (GST) activity was determined in the protein extracts following established methods. Aliquots of the enzyme extract were incubated with 1-chloro-2,4-dinitrobenzene (CDNB), or monochlorobimane. Controls lacking enzyme or GSH were measured. - Pitman chamber experiments. Ten days old barley plants or detached roots were inserted into special incubation chambers, either complete with tips or decapitated, as well as 10 days old barley plants without root tips. Compartment A was filled with a transport medium and GSH conjugate or L-cysteine conjugate. Compartments B and C contained sugar free media. Samples were taken from the root tip containing compartment C and the amount of conjugate transported was determined spectro-photometrically. Results: The transport in roots is unidirectional towards the root tips and leads to exsudation of the conjugates at rates between 20 and 200 nmol min-1. The microscopic studies have been complemented by transport studies in small root chambers and spectroscopic quantification of dinitrobenzene-conjugates. The latter experiments confirm the microscopic studies. Furthermore it was shown that glutathione conjugates are transported at higher rates than cysteine conjugates, despite of their higher molecular weights. This observation points to the existence of glutathione specific carriers and a specific role of glutathione in the root. Discussion: It can be assumed that long distance transport of glutathione conjugates within the plant proceeds like GSH or amino acid transport in both, phloem and xylem. The high velocity of this translocation of the GS-X is indicative of an active transport. For free glutathione, a rapid transport-system is essential because an accumulation of GSH in the root tip inhibits further uptake of sulfur. Taking into account that all described MRP transporters and also the GSH plasmalemma ATPases have side activities for glutathione derivatives and conjugates, co-transport of these xenobiotic metabolites seems credible. - On the other hand, when GS-B was applied to the root tips from the outside, no significant uptake was observed. Thus it can be concluded that only those conjugates can be transported in the xylem which are formed inside the root apex. Having left the root once, there seems to be no return into the root vessels, probably because of a lack of inward directed transporters. Conclusions: Plants seem to possess the capability to store glutathione conjugates in the vacuole, but under certain conditions, these metabolites might also undergo long range transport, predominantly into the plant root. The transport seems dependent on specific carriers and is unidirectional, this means that xenobiotic conjugates from the rhizosphere are not taken up again. The exudation of xenobiotic metabolites offers an opportunity to avoid the accumulation of such compounds in the plant. Recommendations and Perspectives: The role of glutathione and glutathione related metabolites in the rhizosphere has not been studied in any detail, and only scattered data are available on interactions between the plant root and rhizosphere bacteria that encounter such conjugates. The final fate of these compounds in the root zone has also not been addressed so far. It will be interesting to study effects of the exuded metabolites on the biology of rhizosphere bacteria and fungi.     

Endpoint ‘floating leaves’ of <Emphasis Type="Italic">Potamogeton natans</Emphasis>: A new method to evaluate the development of macrophytes in pond mesocosms

Goal, Scope and Background One of the advantages of long-term mesocosm experiments as compared to short-term standard toxicity tests in the laboratory is the potential for detecting secondary effects due to the interaction of species and recovery with biomass of macrophytes being an important endpoint. However, generating biomass data by harvesting is often laborious, time-consuming, costly and restricted to the end of the experiment. Moreover, valuable information may get lost, in particular in single application studies, since maximal primary effects and secondary effects or recovery occur per se at different times. Potamogeton natans was used as an example in order to test whether number and area of floating leaves can be reliably measured and be used as intermediate and final endpoints in mesocosm effect studies. Methods Digital photos, which were taken of the water surface in the course of an indoor pond mesocosm study on herbicide effects, were subjected to image analysis. The results were compared to wet weight and ash-free dry weight of Potamogeton at the end of the herbicide study. Results and Discussion Both number and area of floating leaves indicated the same herbicide effects as wet weight and ash-free dry weight of Potamogeton. Error introduced by the different work steps is small and can be further minimised by a number of method improvements. Recommendations and Perspectives In indoor mesocosm studies, errors due to the perspective adjustment may be circumvented by taking the photos perpendicular to the water surface. Correction for lens aberration, identical light conditions and the use of fluorescence images are considered promising. Field applications are proposed.     

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.