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Bioremediation of endosulfan contaminated soil and water -- optimization of operating conditions in laboratory scale reactors.

A mixed bacterial culture consisted of Staphylococcus sp., Bacillus circulans-I and -II has been enriched from contaminated soil collected from the vicinity of an endosulfan processing industry. The degradation of endosulfan by mixed bacterial culture was studied in aerobic and facultative anaerobic conditions via batch experiments with an initial endosulfan concentration of 50mg/L. After 3 weeks of incubation, mixed bacterial culture was able to degrade 71.58+/-0.2% and 75.88+/-0.2% of endosulfan in aerobic and facultative anaerobic conditions, respectively. The addition of external carbon (dextrose) increased the endosulfan degradation in both the conditions. The optimal dextrose concentration and inoculum size was estimated as 1g/L and 75mg/L, respectively. The pH of the system has significant effect on endosulfan degradation. The degradation of alpha endosulfan was more compared to beta endosulfan in all the experiments. Endosulfan biodegradation in soil was evaluated by miniature and bench scale soil reactors. The soils used for the biodegradation experiments were identified as clayey soil (CL, lean clay with sand), red soil (GM, silty gravel with sand), sandy soil (SM, silty sand with gravel) and composted soil (PT, peat) as per ASTM (American society for testing and materials) standards. Endosulfan degradation efficiency in miniature soil reactors were in the order of sandy soil followed by red soil, composted soil and clayey soil in both aerobic and anaerobic conditions. In bench scale soil reactors, endosulfan degradation was observed more in the bottom layers. After 4 weeks, maximum endosulfan degradation efficiency of 95.48+/-0.17% was observed in red soil reactor where as in composted soil-I (moisture 38+/-1%) and composted soil-II (moisture 45+/-1%) it was 96.03+/-0.23% and 94.84+/-0.19%, respectively. The high moisture content in compost soil reactor-II increased the endosulfan concentration in the leachate. Known intermediate metabolites of endosulfan were absent in all the above degradation studies.

Bacillus↗

Starved air combustion-solidification/stabilization of primary chemical sludge from a tannery.

The high concentration of trivalent chromium along with organic/inorganic compounds in tannery sludge causes severe ground water contamination in the case of land disposal and chronic air pollution during incineration. In the present investigation, the sludge was subjected to flow-through column test to evaluate the concentration of leachable organics (tannin, COD and TOC) and heavy metal ions (Cr(3+), Fe(2+)) present in it. The dried sludge was incinerated at 800 degrees C in an incinerator under starved oxygen supply (starved-air combustion) to prevent the conversion of Cr(3+) to Cr(6+). The efficiency of starved air combustion was studied under different loading rates of sludge. The calcined sludge was solidified/stabilized using fly ash and Portland cement/gypsum. The solidified bricks were tested for unconfined compressive strength and heavy metal leaching. Unconfined compressive strength of the blocks was in the range of 83-156 kg/cm(2). The stabilization of chromium (III) in the cement gel matrix was confirmed with scanning electron microscopy (SEM) and X-ray energy dispersive spectroscopy (EDX). Leachability studies on solidified bricks were carried out to determine the metal fixation and dissolved organic (as COD) concentration in the leachate.

Adsorption↗

Assessment of the multi-scale leaching behaviour of compacted coal fly ash.

Peer experimental-modelling tools were developed and applied in the case of coal fly ashes with the aim to assess the leaching behaviour of ash compacted layers in a use scenario. Laboratory-scale (dissolution kinetics, ANC test, column percolation) and field pilot experimental studies (release monitoring during 18 month, hydrodynamic study, ANC on 44 month leached waste) were performed in order to identify and quantify the main transport phenomena and chemical processes. A quantitative geochemical model was developed taking into account equilibrium chemical reactions as well as kinetic processes for silicate phases like albite, K-feldspar and Ca-olivine. Phases like BaHAsO(4) and a solid solution Ba(x)Sr(1-x)(SO(4))(y)(CrO(4))(1-y) were proposed to explain the complex leaching behaviour of As, Cr, Ba, S; the soluble CaMoO(4) seems to control the Mo concentration. At neutral and acid pH, the model of surface complexation on ferric hydroxides was added for describing the behaviour of As, Cr, and Mo. At each scale the dynamic processes were identified and quantified by modelling. During the first contact with water an equilibration time of about 10 days was identified and then considered in all other laboratory experiments (ANC, column percolation). The hydrodynamic properties of compacted fly ashes were identified: a high water retention capacity (97% of the pores are still filled after draining under normal pressure), a flow regime close to plug type, a low fraction of stagnant zones (<0.03%). The scenario factors like carbonation and rainfall play an important role on the leaching behaviour at field scale. The carbonation diminishes the leachate pH from 11 to 8.5. The alternation of rain periods determines an apparent batch behaviour which slows down the outflow of the initial soluble fraction in pore water, if compared with the laboratory percolation column. The coupled geochemical-transport model was validated by comparison of the simulation results on ANC data obtained on the waste after 44 months of leaching under natural conditions.

Acids↗

Heavy metals removal from automobile shredder residues (ASR).

The fate of heavy metals during a separation process for automobile shredder residues (ASR) was investigated. A washing method to remove heavy metals from the ASR was also investigated. Although the separation process was not designed for removal of heavy metals, but for the recovery of reusable materials, the heavy metal content in the ASR was efficiently decreased. The concentrations of Pb, Cr and Cd in ASR were effectively reduced by a nonferrous metals removal process, and the As concentration was reduced by the removal of light dusts during the separation process. Five heavy metals (As, Se, Pb, Cr, Cd) remaining in the ASR after the separation process satisfied the content criteria of the Environmental Quality Standards for Soil (EQSS), while the concentrations of As, Se, Pb in the leachate from the remaining ASR did not satisfy the elution criteria of the EQSS. After additional washing of the remaining ASR with a pH 1 acid buffer solution, the As, Se, and Pb concentrations satisfied the EQSS for elution. These results indicate that an ASR residue can be safely recycled after a separation process, followed by washing at acidic pH.

Automobiles↗

Hazardous jarosite use in developing non-hazardous product for engineering application.

Jarosite released from zinc metal extraction process is hazardous in nature and its world wide disposal has become a major environmental concern. In this study, an attempt has been made to immobilise and recycle the jarosite released from Hindustan Zinc Limited, India, using CCRs, so called fly ash, and clay soil. Results revealed that the particle size of jarosite was finer than that of CCRs and had higher porosity and water holding capacity due to fine textured materials resulting in high surface area (10,496.18 +/- 30.90 cm(2)/g). Jarosite contain higher concentration of toxic elements (lead, zinc, sulphur, cadmium, chromium and copper) than that of CCRs. Concentrations of radionuclides such as (226)Ra, (40)K and (228)Ac in jarosite found less than in CCRs are similar to that of soil. Statistically designed experiments on solidified/stabilised (s/s) sintered jarosite--CCRs products confirmed that the compressive strength of jarosite bricks reached as high as 140 kg/cm2 with 14.5% water absorption capacity at the combination of 3:1 ratio of jarosite and clay, respectively, but, concentrations of all the toxic elements recommended by United States Environmental Protection Agency (USEPA)--Toxicity Leachate Characteristics Procedure (TCLP) standard are not within the permissible limits. However, it is confirmed that the toxic elements leaching potentials of s/s-sintered products developed using 2:1 jarosite clay ratio with 15% CCRs comply with the USEPA-TCLP limits and also meet the quality for engineering applications.

Adsorption↗

Stabilization/solidification of lead-contaminated soil using cement and rice husk ash.

This paper presents the findings of a study on solidification/stabilization (S/S) of lead-contaminated soil using ordinary Portland cement (OPC) and rice husk ash (RHA). The effects of varying lead concentrations (in the form of nitrates) in soil samples on the physical properties of their stabilized forms, namely unconfined compressive strength (UCS), setting times of early mixtures and changes in crystalline phases as well as chemical properties such as leachability of lead, pH and alkalinity of leachates are studied. Results have indicated that usage of OPC with RHA as an overall binder system for S/S of lead-contaminated soils is more favorable in reducing the leachability of lead from the treated samples than a binder system with standalone OPC. On the other hand, partial replacement of OPC with RHA in the binder system has reduced the UCS of solidified samples.

Alkalies↗

Feasibility study of using brick made from municipal solid waste incinerator fly ash slag.

This study deals with the effect of MSWI slag on fired clay bricks. Brick samples were heated to temperatures which varied from 800 to 1,000 degrees C for 6h, with a heating rate of 10 degrees C/min. The material properties of the resultant material then determined, including speciation variation, loss on ignition, shrinkage, bulk density, 24-h absorption rate and compressive strength. Toxicity Characteristic Leaching Procedure tests were also conducted. The results indicate that the heavy metal concentrations in the leachates met the current regulatory thresholds. Increasing the amount of MSWI slag resulted in a decrease in the water absorption rate and an increase in the compressive strength of the MSWI-slag bricks. The 24-h absorption rate and compressive strength of the MSWI-slag brick made from samples containing slag sintered at 1,000 degrees C all met the Chinese National Standard (CNS) building requirements for second-class brick. The addition of MSWI slag to the mixture reduced the degree of firing shrinkage. This indicates that MSWI slag is indeed suitable for the partial replacement of clay in bricks.

Adsorption↗

Biosorption of cadmium by various types of dried sludge: an equilibrium study and investigation of mechanisms.

Batch equilibrium sorption experiments were used for screening for cost-effective four types of sludge, which were DWS (drinking water treatment plant sludge), LLS (landfill leachate sludge), ADSS (anaerobically digested sewage sludge), and SS (sewage sludge). SS removed cadmium most efficiently from aqueous solution (0.38 mmol/g), and showed the highest desorption efficiency (26.3%). Only the SS can be fitted by Langmuir isotherm model (r2 = 0.996). The FT-IR spectra of SS and cadmium loaded SS indicated that carboxyl groups were major binding sites of cadmium binding sites. In kinetic experiment, it was found that the uptake of the metal by the SS was accompanied with proton release, indicating that the metal binding occurs via an ion exchange as well as by electrostatic interaction between carboxylate groups and cadmium ions. This sorbent may have a potential for use as high-value biosorbent of heavy metals and it deserves further investigations into the details of practical application, for example on the development of desorption methods and on sorption process optimization.

Adsorption↗

Test method selection, validation against field data, and predictive modelling for impact evaluation of stabilised waste disposal.

In setting criteria for landfill classes in Annex II of the EU Landfill Directive, it proved to be impossible to derive criteria for stabilised monolithic waste due to the lack of information on release and release controlling factors in stabilised waste monofills. In this study, we present a scientific basis, which enables a realistic description of the environmental impact of stabilised waste landfills. The work in progress involves laboratory testing of different stabilisation recipes, pilot scale studies on site and evaluation of field leachate from a full-scale stabilisation landfill. We found that the pHs in run-off and in percolate water from the pilot experiment are both around neutral. The neutral pH in run-off is apparently caused by the rapid atmospheric carbonation of those alkaline constituents that are released. The soil, used as a liner protection layer, controls the release to the subsurface below the landfill. This soil layer buffers pH and binds metals. The modelling results show that the chemistry is understood rather well. Differences between predicted and actual leaching might then be attributed to discrepancies in the description of sorption processes, complexation to organic matter and/or kinetic effects in the leaching tests. We conclude that this approach resulted in a new scientific basis for environmental impact assessment of stabilised waste landfills. The integrated approach has already resulted in a number of very valuable observations, which can be used to develop a sustainable landfill for monolithic waste and to provide guidance for the management of waste to be stabilised (e.g. improved waste mix design).

Hazardous Waste↗

Leaching behaviour of low level organic pollutants contained in cement-based materials: experimental methodology and modelling approach.

The aim of this paper is the investigation of the leaching behaviour of different porous materials containing organic pollutants (PAH: naphthalene and phenanthrene). The assessment methodology of long term leaching behaviour of inorganic materials was extended to cement solidified organic pollutants. Based on a scenario-approach considering environmental factors, matrix and pollutants specificities, the applied methodology is composed of adapted equilibrium and dynamic leaching tests. The contributions of different physical and chemical mechanisms were identified and the leaching behaviour was modelled. The physical parameters of the analysed reference and polluted materials are similar. A difference in the pore size distribution appears for higher naphthalene content. The solubility of the PAH contained in the material is affected by the ionic strength and by the presence of a co-solvent; the solution pH does not influence PAH solubility. The solubility of the major mineral species is not influenced by the presence of the two PAH nor by the presence of the methanol as co-solvent in the range of the tested material compositions. In the case of the leaching of a monolith material the main transport mechanism is the diffusion in the porous system. For both mineral and organic species we observed at least two dynamic domains. At the beginning of the leaching process the released flux is due to the surface dissolution and to the diffusion of the main quantity dissolved in the initial pore solution. The second period is governed by a stationary regime between dissolution in pore water and diffusion. The model, coupling transport and chemical phenomena in the pore solution, at the monolith surface and in the leachate simulates satisfactory the release for both mineral and organic species.

Adsorption↗

Effects of insufficient air injection on methanogenic Archaea in landfill bioreactor.

In this study, methanogenic Archaea diversity in an aerated landfill bioreactor filled with co-disposed incineration bottom ashes and shredded incombustible wastes was monitored and analyzed as a function of time using molecular techniques. Besides, the effects of insufficient air injection on the bioreactor performance and methanogenic diversity were evaluated thoroughly. Results indicated that rapid bio-stabilization of solid waste are possible with aerated landfill bioreactor at various oxygen and oxidation reduction potential levels. Slot-blot hybridization results of leachate samples collected from aerated landfill bioreactor showed that archaeal and bacterial activities increased as stabilization accelerated and bacterial populations constituted almost 95% of all microorganisms. The results of slot-blot hybridization and phylogenetic analysis based on 16S rRNA gene revealed that Methanobacteriales and Methanomicrobiales were dominant species at the beginning while substituted by Methanosarcina-related methanogens close to the end of the operation of bioreactor.

Air↗

Tree species (Picea abies and Fagus sylvatica) effects on soil water acidification and aluminium chemistry at sites subjected to long-term acidification in the Ore Mts., Czech Republic.

The effect of European beech (Fagus sylvatica) and Norway spruce (Picea abies) on acid deposition and soil water chemistry was studied at a site in the Ore Mts., Czech Republic, that has been subjected to decades of elevated acidic deposition. Dry deposition onto the spruce canopy significantly increased acid input to the soil in comparison to the beech canopy. As a result soil waters were more acidic; Al, SO4(2-), and NO3- concentrations were significantly higher; and Ca and K concentrations were lower in the spruce stand than in the beech stand. The concentrations of potentially toxic inorganic aluminium (Al(in)) were, on average, three times higher in the spruce stand than in the beech stand. Thus, Al played a major role in neutralizing acid inputs to mineral soils in the spruce stand. Despite the higher dissolved organic carbon (DOC) concentrations in spruce organic soil solutions, organic Al (Al(org)) accounted for only 30% of total Al (Al(tot)), whereas in beech organic soil solutions Al(org) was 60% of Al(tot). Soil waters in the beech stand exhibited Al(in) concentrations close to solubility with jurbanite (Al(SO4)OH.5H2O). The more acidic soil waters in the spruce stand were oversaturated with respect to jurbanite. The Bc/Al(in) ratio (Bc = Ca + Mg + K) in O horizon leachate was 4.6 and 70 in spruce and beech stands, respectively. In beech mineral soil solutions, the Bc/Al(in) ratio declined significantly to about 2. In the spruce stand, mineral soil solutions had Bc/Al(in) values below the critical value of 1. The observed Bc/Al(in) value of 0.4 at 30 cm depth in the spruce stand suggests significant stress for spruce rooting systems. A more favourable value of 31 was observed for the same depth in the beech stand. The efficiency of the spruce canopy in capturing acidic aerosols, particulates, and cloud water has resulted in the long-term degradation of underlying soils as a medium for sustainable forest growth.

Journal Article↗

Time dependent calibration of a sediment extraction scheme.

Sediment extraction methods to quantify metal concentration in aquatic sediments usually present limitations in accuracy and reproducibility because metal concentration in the supernatant is controlled to a large extent by the physico-chemical properties of the sediment that result in a complex interplay between the solid and the solution phase. It is suggested here that standardization of sediment extraction methods using pure mineral phases or reference material is futile and instead the extraction processes should be calibrated using site-specific sediments before their application. For calibration, time dependent release of metals should be observed for each leachate to ascertain the appropriate time for a given extraction step. Although such an approach is tedious and time consuming, using iron extraction as an example, it is shown here that apart from quantitative data such an approach provides additional information on factors that play an intricate role in metal dynamics in the environment. Single step ascorbate, HCl, oxalate and dithionite extractions were used for targeting specific iron phases from saltmarsh sediments and their response was observed over time in order to calibrate the extraction times for each extractant later to be used in a sequential extraction. For surficial sediments, an extraction time of 24 h, 1 h, 2 h and 3 h was ascertained for ascorbate, HCl, oxalate and dithionite extractions, respectively. Fluctuations in iron concentration in the supernatant over time were ubiquitous. The adsorption-desorption behavior is possibly controlled by the sediment organic matter, formation or consumption of active exchange sites during extraction and the crystallinity of iron mineral phase present in the sediments.

Calibration↗

Mutagens in contaminated soil: a review.

The intentional and accidental discharges of toxic pollutants into the lithosphere results in soil contamination. In some cases (e.g., wood preserving wastes, coal-tar, airborne combustion by-products), the contaminated soil constitutes a genotoxic hazard. This work is a comprehensive review of published information on soil mutagenicity. In total, 1312 assessments of genotoxic activity from 118 works were examined. The majority of the assessments (37.6%) employed the Salmonella mutagenicity test with strains TA98 and/or TA100. An additional 37.6% of the assessments employed a variety of plant species (e.g., Tradescantia clone 4430, Vicia faba, Zea mays, Allium cepa) to assess mutagenic activity. The compiled data on Salmonella mutagenicity indicates significant differences (p<0.0001) in mean potency (revertents per gram dry weight) between industrial, urban, and rural/agricultural sites. Additional analyses showed significant empirical relationships between S9-activated TA98 mutagenicity and soil polycyclic aromatic hydrocarbon (PAH) concentration (r2=0.19 to 0.25, p<0.0001), and between direct-acting TA98 mutagenicity and soil dinitropyrene (DNP) concentration (r2=0.87, p<0.0001). The plant assay data revealed excellent response ranges and significant differences between heavily contaminated, industrial, rural/agricultural, and reference sites, for the anaphase aberration in Allium cepa (direct soil contact) and the waxy locus mutation assay in Zea mays (direct soil contact). The Tradescantia assays appeared to be less responsive, particularly for exposures to aqueous soil leachates. Additional data analyses showed empirical relationships between anaphase aberrations in Allium, or mutations in Arabidopsis, and the 137Cs contamination of soils. Induction of micronuclei in Tradescantia is significantly related to the soil concentration of several metals (e.g., Sb, Cu, Cr, As, Pb, Cd, Ni, Zn). Review of published remediation exercises showed effective removal of genotoxic petrochemical wastes within one year. Remediation of more refractory genotoxic material (e.g., explosives, creosote) frequently showed increases in mutagenic hazard that remained for extended periods. Despite substantial contamination and mutagenic hazards, the risk of adverse effect (e.g., mutation, cancer) in humans or terrestrial biota is difficult to quantify.

Industrial Waste↗

Occurrence of laccases in lichenized ascomycetes of the Peltigerineae.

Following our previous findings of high extracellular redox activity in lichens, the results of the work presented here identify the enzymes involved as laccases. Despite numerous data on laccases in fungi and flowering plants, this is the first report of the occurrence of laccases in lichenized ascomycetes. Extracellular laccase activity was measured in 40 species of lichens from different taxonomic groupings and contrasting habitats. Out of 20 species tested from suborder Peltigerineae, 18 displayed laccase activity, while activity was absent in species tested from other lichen groups. Identification of the enzymes as laccases was confirmed by the ability of lichen leachates to readily metabolize substrates such as 2,2'-azino(bis-3-ethylbenzthiazoline-6-sulfonate) (ABTS), syringaldazine and o-tolidine in the absence of hydrogen peroxide, sensitivity of the enzymes to cyanide and azide, the enzymes having typical laccase pH and temperature optima, and an absorption spectrum with a peak at 614nm. Desiccation and wounding stimulated laccase activity. Laccase activity was not increased after treatment with normal inducers of laccase synthesis, suggesting that they are constitutively expressed. Electrophoresis showed that the active form of laccase from Peltigera malacea was a tetramer with an unusually high molecular mass of 340kDa and an isoelectric point (pI) of 4.7. The finding of abundant extracellular redox enzymes known to actively produce reactive oxygen species suggest that their roles may include increasing nutrient supply to lichens by delignification, and deterring pathogens by contributing to the oxidative burst. Furthermore, once released into the environment, they may participate in the carbon cycle by facilitating the breakdown or formation of humic substances.

Ascomycota↗

Allelochemicals from Stauranthus perforatus, a Rutaceous tree of the Yucatan Peninsula, Mexico.

Aqueous leachates and a CHCl3-MeOH (1:1) extract of roots of Stauranthus perforatus showed a significant phytotoxic effect on Amaranthus hypochondriacus and Echinochloa crus-galli. Bioassay-directed fractionation of the active organic extract led to the isolation and characterization of ten secondary metabolites, which included two pyranocoumarins [xanthyletin (1) and 3-(1',1'-dimethylallyl)-xanthyletin (2)], four furanocoumarins [chalepensin (3), ammirin (4), chalepin (5) and 2'-isopropyl-psoralene (6)], two lignans [asarinin (7) and fargesin (8)], one sesquiterpene [4,5-epoxi-beta-caryophyllene (9)], and one alkamide [pellitorine (10)]. From these compounds, 2'-isopropyl-psoralene (6) or anhydromarmesin, is reported for the first time as a natural product, whereas compounds 4-10 are now reported as being present in S. perforatus. Metabolites 1, 3-5 and 10 caused significant inhibition of radicle growth of A. hypochondriacus and E. crus-galli. Furthermore, in a greenhouse experiment the decomposition of the leaves and roots in the soil had a significant inhibitory effect on the growth of weeds. The allelopathic action of the decomposition of roots was evident up to the sixth week of the experiment. The effect of leaves was comparable to that of DPCA (dimethyl tetrachloroterephthalate), a commercial herbicide. Finally different concentrations of Stauranthus root powder were combined with maize kernels and used to feed corn weevil. The treatments resulted in high mortality of this insect.

Animals↗

Plant-associated Pseudomonas populations: molecular biology, DNA dynamics, and gene transfer.

Bacteria of the genus Pseudomonas are usual colonizers of plant leaves, roots, and seeds, establishing at relatively high cell densities on plant surfaces, where they aggregate and form microcolonies similar to those observed during biofilm development on abiotic surfaces. These plant-associated biofilms undergo chromosomal rearrangements and are hot spots for conjugative plasmid transfer, favored by the close proximity between cells and the constant supply of nutrients coming from the plant in the form of exudates or leachates. The molecular determinants known to be involved in bacterial colonization of the different plant surfaces, and the mechanisms of horizontal gene transfer in plant-associated Pseudomonas populations are summarized in this review.

Chromosomes, Bacterial↗

Groundwater pollution on the Zambian Copperbelt: deciphering the source and the risk.

The protection of groundwater resources is of great importance in many semi-arid and sub-tropical environments. The Copperbelt of Zambia is one such environment and due to the high proportion of tailings impoundments, residue heaps, high-density informal settlements and extensive sulfidic ore deposits in the region, its groundwater resources are under threat of anthropogenic or geogenic pollution. One such pollutant plume is investigated in this study, to determine its origin, rate of progression and the environmental and health risk it poses. Geological and geochemical investigation strongly suggests an upslope tailings impoundment as the source of contaminants, with the edge of the pollution plume lying 500-700 m downstream of the impoundment. Although cobalt, nickel and zinc concentrations were elevated within the polluted groundwater, the concentrations are low as a result of sulfide precipitation and adsorption within the aquifer, and meets guidelines for drinking water quality. Attenuation of heavy metals is linked to tailings dam and aquifer pH, with the high buffering capacity of each implying that these processes of attenuation are likely to continue removing harmful metals from the aquifer. Thus, it appears unlikely that the contaminated groundwater will present a major environmental risk at this site. However, tailings impoundments are widespread throughout the Copperbelt: sites with low tailings dam buffer capacity and in catchments on crystalline bedrock geology, groundwater pollution through tailings dam leachate may liberate high concentrations of heavy metals into the shallow groundwater, potentially posing a serious human health risk to the communities using the water resources and an environmental risk to the downstream ecosystems.

Conservation of Natural Resources↗