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Comparison between electrocoagulation and chemical precipitation for metals removal from acidic soil leachate.

This paper provides a quantitative comparison between electrocoagulation and chemical precipitation based on heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) removal from acidic soil leachate (ASL) at the laboratory pilot scale. Chemical precipitation was evaluated using either calcium hydroxide or sodium hydroxide, whereas electrocoagulation was evaluated via an electrolytic cell using mild steel electrodes. Chemical precipitation was as effective as electrocoagulation in removing metals from ASL having low contamination levels (30 mg Pbl(-1) and 18 mg Znl(-1)). For ASL enriched with different metals (each concentration of metals was initially adjusted to 100 mg l(-1)), the residual Cr, Cu, Pb and Zn concentrations at the end of the experiments were below the acceptable level recommended for discharge in sewage urban works (more than 99.8% of metal was removed) using either electrocoagulation or chemical precipitation. Cd was more effectively removed by electrochemical treatment, whereas Ni was easily removed by chemical treatment. The cost for energy, chemicals and disposal of metallic residue of electrocoagulation process ranged from USD 8.83 to 13.95 tds(-1), which was up to five times lower than that recorded using chemical precipitation. Highly effective electrocoagulation was observed as the ASL was specifically enriched with high concentration of Pb (250-2000 mg Pbl(-1)). More than 99.5% of Pb was removed regardless of the initial Pb concentration imposed in ASL and, in all cases, the residual Pb concentrations (0.0-1.44 mg l(-1)) were below the limiting value (2.0 mg l(-1)) for effluent discharge in sewage works.

Electrochemistry↗

Gonad development and plasma steroid profiles by HRGC/HRMS during one reproductive cycle in reference and leachate-exposed female perch (Perca fluviatilis).

Endocrine processes were studied in reference female perch (Perca fluviatilis) from Lake Djursjön and in leachate-exposed females from Lake Molnbyggen during one reproductive cycle. A high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) technique enabled the analysis of circulating sex steroids [progesterone (P), 17alpha-hydroxyprogesterone (17alpha-OHP), androstenedione (A), testosterone (T), estrone (E1), and 17beta-estradiol (E2)], the maturation-inducing hormone (MIH) 17alpha,20beta-dihydroxy-4-pregnen-3-one (17alpha,20beta-P), and glucocorticoids [11-deoxycortisol (11-DC) and cortisol]. Body and organ measurements, ratio of sexually mature (SM) females, and frequencies of body lesions, were also recorded. High frequencies of body lesions and a low ratio of SM females were generally found in Molnbyggen. These females also had lower gonadosomatic index (GSI) and liver-somatic index (LSI) in the early stages of vitellogenesis, indicating either a delayed onset of oogenesis or an impaired vitellogenesis. Non-reproducing females from both lakes showed a similar LSI cycle as SM females. Increasing T and A levels in SM females from Djursjön coincided with the GSI peak at the time of spawning. These two androgens were on several occasions lower in SM females from Molnbyggen, possibly the result of a disrupted 17,20-lyase activity of the P450 17alpha enzyme because only minor effects were observed on circulating P and 17alpha-OHP levels. E2 and E1 levels increased during vitellogenesis in females from both lakes, with E1 levels more closely resembling the peaks of A and GSI. Peak levels of 17alpha,20beta-P at the time of spawning confirmed its function as the MIH in perch, while the simultaneous peak of 11-DC suggests that it also may be involved in final maturation of the oocytes.

Animals↗

Stochastic modelling of landfill leachate and biogas production incorporating waste heterogeneity. Model formulation and uncertainty analysis.

A mathematical model simulating the hydrological and biochemical processes occurring in landfilled waste is presented and demonstrated. The model combines biochemical and hydrological models into an integrated representation of the landfill environment. Waste decomposition is modelled using traditional biochemical waste decomposition pathways combined with a simplified methodology for representing the rate of decomposition. Water flow through the waste is represented using a statistical velocity model capable of representing the effects of waste heterogeneity on leachate flow through the waste. Given the limitations in data capture from landfill sites, significant emphasis is placed on improving parameter identification and reducing parameter requirements. A sensitivity analysis is performed, highlighting the model's response to changes in input variables. A model test run is also presented, demonstrating the model capabilities. A parameter perturbation model sensitivity analysis was also performed. This has been able to show that although the model is sensitive to certain key parameters, its overall intuitive response provides a good basis for making reasonable predictions of the future state of the landfill system. Finally, due to the high uncertainty associated with landfill data, a tool for handling input data uncertainty is incorporated in the model's structure. It is concluded that the model can be used as a reasonable tool for modelling landfill processes and that further work should be undertaken to assess the model's performance.

Biodegradation, Environmental↗

Anaerobic treatment of sludge from a nitrification-denitrification landfill leachate plant.

The viability of anaerobic digestion of sludge from a MSW landfill leachate treatment plant, with COD values ranging between 15,000 and 19,400mg O(2)dm(-3), in an upflow anaerobic sludge blanket reactor was studied. The reactor employed had a useful capacity of 9l, operating at mesophilic temperature. Start-up of the reactor was carried out in different steps, beginning with diluted sludge and progressively increasing the amount of sludge fed into the reactor. The study was carried out over a period of 7 months. Different amounts of methanol were added to the feed, ranging between 6.75 and 1cm(3)dm(-3) of feed in order to favour the growth of methanogenic flora. The achieved biodegradation of the sludge using an upflow anaerobic sludge blanket Reactor was very high for an HRT of 9 days, obtaining decreases in COD of 84-87% by the end of the process. Purging of the digested sludge represented approximately 16% of the volume of the treated sludge.

Anaerobiosis↗

Pretreated waste landfilling: relation between leachate characteristics and mechanical behaviour.

The present paper presents a part of a wider research effort aiming at studying the long-term behaviour of different pre-treated wastes once landfilled; in particular, this paper deals with the analysis of settlements and their correlation with the main leachate biochemical parameters (BOD, COD and pH). The municipal solid waste organic fraction (MSWOF) and bottom ash (BA) from incineration of municipal solid waste (MSW) were considered in the study and used to set up different semi-pilot landfill plants. Particularly, the FT plant contained 90 days aerobically biostabilized MSWOF, the FP plant was filled with 15 days aerobically biostabilized MSWOF and the MX plant with a 30-70% (by weight) mixture of BA and the same MSWOF used in the FP plant. The data obtained showed a faster mechanical and biological stabilization of the FT and MX plants, due to the less biodegradable organic fraction content initially present in the FT plant and to the presence of BA, having a stabilizing effect, in the MX plant. Besides, similar behaviour of FT and MX was observed, and also a strong correlation between the settlement and the biochemical parameters time profiles was identified.

Hydrogen-Ion Concentration↗

Stabilized leachates: ozone-activated carbon treatment and kinetics.

Ozone has been used as a pre-oxidation step for the treatment of stabilized leachates. Given the refractory nature of this type of effluents, the conversion of some wastewater quality parameters has been moderate after 1 h of ozonation (i.e. 30% chemical oxygen demand (COD) depletion). Ozone uptake was calculated in the interval 1.3-1.5 g of ozone per gram of COD degraded. An optimum dose of ozone has been experienced in terms of biodegradability of the processed effluent (60 min of treatment, 1 x 10(-3) mol L(-1) ozone inlet feeding concentration and 50 L h(-1) gas flow-rate). pH and other typical hydroxyl radical generator systems exerted no influence on the efficiency of the process, suggesting the negligible role played by the indirect route of oxidation (generation of hydroxyl radicals). The ozonated effluent was thereafter treated in a second adsorption stage by using a commercial activated carbon. Removal levels up to 90% of COD in approximately 120 h were experienced for adsorbent dosages of 30 g L(-1). Both steps, the single ozonation and the adsorption stage have been modelled by using different pseudoempirical models.

Carbon↗

A laboratory study of landfill-leachate transport in soils.

Continuous flow experiments were conducted using sand-packed columns to investigate the relative significance of bacterial growth, metal precipitation, and anaerobic gas formation on biologically induced clogging of soils. Natural leachate from a local municipal landfill, amended with acetic acid, was fed to two sand-packed columns operated in upflow mode. Degradation of the influent acetic acid resulted in the production of methane and carbon dioxide, and simultaneous reduction of manganese, iron, and sulphate. Subsequent increase in the influent acetic acid concentration from 1750 to 2900 mg/l, and then to 5100 mg/l, led to rapid increase in the dissolved inorganic carbon, solution pH, and soil-attached biomass concentration at the column inlet, which promoted the precipitation of Mn(2+) and Ca(2+) as carbonate, and Fe(2+) as sulphide. An influent acetic acid concentration of 1750 mg/l decreased the soil's hydraulic conductivity from an initial value of 8.8 x 10(-3)cm/s to approximately 7 x 10(-5)cm/s in the 2-6 cm section of the column. Increasing the influent acetic acid to 5100 mg/l only further decreased the hydraulic conductivity to 3.6 x 10(-5)cm/s; rather, the primary effect was to increase the length of the zone experiencing reduced hydraulic conductivity from 0-6 cm to the entire column. As bioaccumulation was limited to the 0-5 cm section of the column, and the effect of metal precipitation was negligible, the reduction on the deeper sections of the column is attributed to gas flow, which was up to 1440 ml/day. Mathematical modelling shows that biomass accumulation and gas formation were equally significant in reducing the hydraulic conductivity, while metal precipitation contributed only up to 4% of the observed reduction.

Acetic Acid↗

Dynamics and influencing factors of heterotrophic bacterial utilization of acetate in constructed wetlands treating woodwaste leachate.

14C-acetate was used as a tracer of substrates for heterotrophic bacteria to investigate the dynamics and influencing factors of bacterial activity in surface flow wetlands treating woodwaste leachate. Epiphytic assimilation and mineralization of acetate increased considerably over three weeks of microbial colonization. No significant longitudinal variation in acetate uptake was found. The temporal variation of bacterial activity was neither correlated to water temperature nor acetic acid concentration. Mineralization percentage varied significantly with acetate uptake rate. Acetate uptake rates of bacterioplankton (408+/-258 microg L(-1) h(-1)), epiphyton (67.7+/-41.7 mg m(-2) h(-1)) and sedimentary bacteria (26.7+/-25.6 microg g(-1) h(-1)) were influenced by the concentrations of organic substrates and inorganic nutrients. Sedimentary bacteria contributed to the majority (55-73%) of the total heterotrophic acetate uptake, while epiphytic bacteria played only a minor role (1-3%). The acetate mineralization percentage of sediment (16%) was much lower than that of water (55%) and epiphyton (64%). Addition of ammonium nitrate fertilizer increased acetate uptake rates significantly, especially for sediment. No remarkable changes in mineralization percentage and the relative importance of water, sediment and epiphyton were found due to fertilization.

Acetates↗

Xenobiotic organic compounds in leachates from ten Danish MSW landfills--chemical analysis and toxicity tests.

A monitoring program comprising chemical analysis and biological toxicity testing of leachate samples from 10 Danish landfills (six engineered and four uncontrolled) revealed the presence of 55 different xenobiotic organic compounds (XOCs) and 10 degradation products of XOCs. The compounds belong to the following groups: BTEX, C3-benzenes, bicyclo compounds, napthalenes, chlorinated aliphatics, phenols (chloro-, methyl-, dimethyl, nonyl-), pesticides, and phthalates. Concentrations of single XOCs ranged from <0.1 to 2220 microg/L. A pesticide screening including 101 different compounds resulted in detection of 18 pesticides and three degradation products. The findings of degradation products of toluene, phenols, phthalates, pesticides, and nonylphenol ethoxylates show that degradation occurred inside the landfills. In biotests with bacteria and algae it was found that the non-volatile organic compounds were toxic as the samples only needed to be pre-concentrated from 1.3 to 9.4 times to give 50% inhibition of the test organisms. One of the ten samples proved to be genotoxic in the umuC test after 141 times pre-concentration. A major part of the organic chemicals causing toxicity remains unknown and it is recommended to combine chemical analyses and biotests in future monitoring programs.

Bacteria↗

Altered steroid metabolism in several teleost species exposed to endocrine disrupting substances in refuse dump leachate.

Endocrine disruption associated with reproductive failure has been reported previously in female perch (Perca fluviatilis) and roach (Rutilus rutilus) from Lake Molnbyggen in Sweden and in female brook trout (Salvelinus fontinalis) from Vadbäcken, a stream emptying into Molnbyggen. Both Molnbyggen and Vadbäcken have been contaminated by toxic leachate from a municipal refuse dump. In this study, female perch were caught in Molnbyggen and the reference lake, Lake Djursjön, to further investigate the endocrine mechanism behind the significant numbers of sexually immature (SIM) female perch in Molnbyggen. Blood plasma analysis of progesterone (P), 17alpha-hydroxyprogesterone (17alpha-OHP), testosterone (T), and 17beta-oestradiol (E2), as well as analysis of brain aromatase activity (P450arom), were carried out. The exceptional high numbers of SIM female perch in Molnbyggen was confirmed in February 1999. In July 1999, at an early stage of oogenesis, perch from Molnbyggen showed significantly decreased gonadosomatic index (GSI) and aromatase activity. The presence of aromatase inhibiting substances in lake sediments were therefore tested in vitro. The aromatase activity was dose-dependently inhibited by clotrimazole, reaching 50% inhibition at a concentration of 0.9 microM. Aromatase inhibiting substances were found both in Molnbyggen and reference sediment extracts, indicating that they were naturally occurring substances and not of anthrophogenic origin. The similar decrease in levels of circulating steroids (P, 17alpha-OHP, T, and E2), aromatase, and GSI therefore suggest that the low aromatase activity is due to down-regulation rather than inhibition. To further investigate the steroidogenesis prior to T, P, and 17alpha-OHP were analysed in perch caught in 1997 and 1998 in Lakes Molnbyggen, Kvarntjärn (downstream), Yxen (upstream), and Djursjön, in female roach caught in Molnbyggen and Djursjön in 1997, and in brook trout caught in Vadbäcken and the reference stream Björntjärnsbäcken in 1998. The absence of differences in P and 17alpha-OHP levels, combined with a significantly lower T level in female perch and roach from Molnbyggen in 1997, could be the result of either increased metabolism and excretion of T, or a disruption downstream of 17alpha-OHP formation. The unaffected P levels and significantly lower 17alpha-OHP levels, together with significantly decreased T and E2 levels, found in adult (>45g) female brook trout from Vadbäcken, further indicated that an altered steroidogenesis downstream of P is one possible mechanism underlying the low T levels and thus the high number of SIM female fish, since too low T levels might be insufficient to activate the brain-pituitary-gonadal axis.

Animals↗

Comparative studies of the leachate of an industrial landfill by gas chromatography-mass spectrometry, liquid chromatography-nuclear magnetic resonance and liquid chromatography-mass spectrometry.

Nowadays, the need to have a realistic characterization of industrial effluents in the environment has become more and more recognized. A palette of different analytical methods both for sample extraction and instrumental analysis are available today, some older, others introduced more recently. The aim of this research is to compare a number of these techniques. To do this we studied a real leachate from an industrial landfill and carried out chemical analyses for organic pollutants, using different extraction methods based on solid-phase extraction and solid-phase microextraction and different instrumental techniques such as GC-MS, LC-MS, NMR and LC-NMR. Results show the performances of the different techniques, which are complementary.

Chromatography, Liquid↗

Determination of triazines in soil leachates by solid-phase microextraction coupled to gas chromatography-mass spectrometry.

A solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) method was developed for the evaluation of the leachability order of selected triazines (propazine, terbuthylazine, sebuthylazine, ametryn, prometryn and terbutryn) in soil/sediment samples (organic carbon content ranging from 0.19 to 0.42%), analysing fractions collected from a soil packed microcolumn elution experiments. The procedure is fast, simple, highly sensitive and solvent free. SPME-GC-MS was also employed for the quantitative determination of triazines in the soil leachate, since the method showed good recovery yield. Detection limits were always better than 1 ng ml(-1). The method was tested on a contaminated landfill top soil. Prometryn and ametryn were identified through their MS spectra and then quantified. Terbuthylazine was used to assess recovery. Results compared well with those obtained by solvent extraction followed by HPLC-UV detection.

Gas Chromatography-Mass Spectrometry↗

The effect of decreased ambient temperature on the biological nitrification and denitrification of a high ammonia landfill leachate.

This research investigated the nitrogen removal capabilities of a pre- and post-denitrification process, when treating sanitary landfill leachate containing an ammonia concentration of over 2200 mg N/L, at operating temperatures down to 10 degrees C. The treatment system employed is generally known as a 4-Stage Bardenpho process. Two parallel systems were operated throughout the study; each system had an aerobic solids retention time of 20 days and an external recycle ratio (return activated sludge) of about 3:1. During the entire experimental period, one system used an internal recycle ratio of about 4:1, while the other system used one of 3:1. Methanol was used as supplementary carbon source for denitrification. When operating temperature was decreased from 20 to 17 degrees C, an approximate 15% decrease in denitrification was immediately experienced within both systems, with no noticeable affect on nitrification. This was an unexpected result. Subsequently, the temperature was further decreased to 14 degrees C, and finally to 10 degrees C. With the temperature at 14 degrees C, aerobic wasting was also stopped and methanol loading was progressively decreased to match actual denitrification requirements. At 10 degrees C, both systems suffered major nitrification and denitrification inhibition. Changes in operating parameters, such as a decrease in influent ammonia and methanol loading, as well as an increase in ambient temperatures, from 10 to 15 degrees C, did not significantly improve overall system performance, within a reasonable time frame. Both denitrification and nitrification problems were mainly attributed to decreased ambient temperature, although other possible factors were noted; at project completion, about 50% of the incoming ammonia was being removed across the system.

Aerobiosis↗

Simultaneous organic and nitrogen removal from municipal landfill leachate using an anaerobic-aerobic system.

An anaerobic-aerobic system including simultaneous methanogenesis and denitrification was introduced to treat organic and nitrogen compounds in immature leachate from a landfill site. Denitrification and methanogenesis were successfully carried out in the anaerobic reactor while the organic removal and nitrification of NH4+,-N were carried out in the aerobic reactor when rich organic substrate was supplied with appropriate hydraulic retention time. The maximum organic removal rate was 15.2 kg COD/m3 d in the anaerobic reactor while the maximum NH4+-N removal rate and maximum nitrification rate were 0.84kg NH4+-N/m3/d and 0.50kg NO3--N/m3/d, respectively, in the aerobic reactor. The pH range for proper nitrification was 6-8.8 in the aerobic reactor. The organic compounds inhibited nitrification so that the organic removal in the anaerobic reactor could enhance the nitrification rate in the following aerobic reactor. The gas production rate was 0.33 m3/kg COD and the biogas compositions of CH4, CO2, and N2 were kept relatively constant, 66-75, 22-32, and 2-3%, respectively.

Aerobiosis↗

Substrate characterisation for a subsurface reactive barrier to treat colliery spoil leachate.

Subsurface permeable reactive barriers (PRB) have been used to successfully treat acidic mine drainage in Canada and offer great potential for doing the same in the United Kingdom. A PRB for the treatment of colliery spoil leachate from a site near Newcastle upon Tyne, UK, has been designed. The selection of the reactive media to be used is of paramount importance, with particular reference to permeability and reactivity. A number of reactive media mixtures containing varying proportions of cattle slurry screenings, green waste compost, calcite limestone chips and pea gravel were prepared and their respective permeabilities and reactivities were investigated. Media mixtures containing 50% 10 mm grade calcite limestone chips showed better alkalinity addition and metals removal than a blank containing 50% pea gravel. A media mixture containing 50% limestone chips and 50% green waste compost showed a 24 h period to achieve maximum addition of alkalinity and maximum removal of acidity and metals. Mixtures containing 25% green waste compost and 25% slurry screenings achieved maximum addition/removal in 4 h. The likely presence of iron sulphide in samples drawn from test vessels during both test runs indicates that bacterial sulphate reduction is occurring in this composite.

Animals↗

Enzymatic treatment of sanitary landfill leachate.

The objective of this investigation was to study the effectiveness of applying enzymes (bioaugmentation) for enhancement of biological treatability of leachates generated in a typical municipal solid waste sanitary landfill. The basic purpose of enzyme use is to enforce the biodecomposition of organic constituents, as well as to reduce nitrogen content. A laboratory-scale sequencing batch (bio)reactor (SBR) was used for the examination of enzymatic application. The effect of different operation strategies on the efficiency of this biological treatment process was studied to optimize performance, especially for the removal of nitrogen compounds and of biodegradable organic matter. It was found that the enzymatic process was able to remove organic matter effectively (expressed as BOD5 and COD) and nitrogen content, color and turbidity.

Biodegradation, Environmental↗

Assessment of metal content and toxicity of leachates from teapots.

Metallic teapots traditionally used in Morocco were investigated for release of toxic metals from the teapots and their toxicity, as determined by MetPAD, a bacterial toxicity test that is specific for heavy metal toxicity. Our data show that some teapots were non-toxic while a few others were highly toxic, as shown by MetPAD. Tea addition reduced somewhat heavy metal toxicity due possibly to the complexing ability of tea. Chemical analysis of teapot leachates showed that some contained zinc and copper. Teapot No. 5, which showed the highest toxicity, also displayed the highest Zn concentration (7.39 mg/l), confirming the toxicity data. Based on estimates of tea consumption in Morocco, we showed that the extra daily burden of Zn ranged from 1.75 to 4.2 mg/day, assuming the maximum zinc concentration of 7.4 mg/l, as found in our study. This represents 3.5-8% of the LOAEL for zinc of 50 mg/day and would not be important as compared to other sources zinc intake.

Chromium↗

Insights into the mechanisms of copper tolerance of a population of black-banded rainbowfish (Melanotaenia nigrans) (Richardson) exposed to mine leachate, using 64/67Cu.

This study investigates the mechanisms of copper tolerance of a population of black-banded rainbowfish (Melanotaenia nigrans) (Richardson). The population has been exposed to elevated copper concentrations for over 40 years, due to leachate from the Rum Jungle uranium/copper mine. At the time of collection the 96 h EC(50) of exposed [E] fish was 8.3 times higher than that of reference [R] fish. The bioconcentration of 64/67Cu in fish was used to investigate the mechanism of copper tolerance in E fish. Both E and R fish were exposed to low (L(Cu), 30 microg Cu l(-1)) and elevated (E(Cu), 300 microg Cu l(-1)) copper concentrations for 24 and 48 h, respectively. Radioactivity was measured at seven or eight time points in four tissue sections: head (including gills, heart and brain), internal organs (including gastrointestinal tract, liver, kidneys and gonads), muscle and whole body. One-compartment bioconcentration models were fit to data and compared using an F-test. Copper concentrations in all tissue sections were significantly (P<0.05) less (up to 50%) in E fish compared with the respective tissue sections of R fish when exposed to both L(Cu) and E(Cu). The exception was copper accumulation in the internal organs, which was not significantly different between E and R fish exposed to E(Cu). The mechanism of copper tolerance was concluded to be reduced copper uptake in the gills, rather than increased binding or elimination. Allozyme electrophoresis was performed to determine if genetic selection had occurred in the E fish population. Allozyme frequencies at the AAT-1 and GPI-1 loci were significantly (P<0.05) different between E and R fish. Heterozygosity was reduced in E fish compared with that of R fish. Collectively these results suggest that genetic selection may have occurred in the E fish population. Consequently, the selection of allozymes less sensitive to copper may be another mechanism of copper tolerance of E fish. This is the first study on the mechanisms of copper tolerance in a wild fish population that has been exposed to elevated copper concentrations. These findings aid the understanding of metal tolerance in fish and emphasise the importance of sample selection and its implication for toxicity testing.

Adaptation, Physiological↗