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Mobility of atrazine from alginate-bentonite controlled release formulations in layered soil.

The mobility of atrazine [6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine] from alginate-bentonite-based controlled release (CR) formulations was investigated by using soil columns. Two CR formulations based on sodium alginate (14.0 g kg(-1), atrazine (6.0 g kg(-1), natural or acid-treated bentonite (50 g kg(-1), and water (924 g kg(-1) were compared to technical grade product and commercial liquid (CL) formulation (Gesaprim 500FW). All herbicide treatments were applied to duplicate layered bed systems simulating the typical arrangement under a plastic greenhouse, which is composed of sand (10 cm), peat (2 cm), amended soil (20 cm) and native soil (20 cm). The columns were leached with 39 cm (1500 ml) and 156 cm (6000 ml) of 0.02 M CaCl2 solution to evaluate the effect of water volume applied on herbicide movement. When 39 cm of 0.02 M CaCl2 solution was applied, there was no presence of herbicide in the leachate for the alginate-bentonite CR treatments. However, 0.11% and 0.14% of atrazine appeared in the leachate when the treatment was carried out with technical grade and CL formulations, respectively. When 156 cm of 0.02 M CaCl2 solution was applied, the use of the alginate-acid treated bentonite CR formulation retards and reduces the presence of atrazine in the leachate as compared to technical product. Analysis of the soil columns showed the highest atrazine concentration in the peat layer. Alginate-bentonite CR formulations might be an efficient system for reducing atrazine leaching in layered soil and thus, it could reduce the risks of pollution of groundwater.

Alginates↗

Distribution of inorganic arsenic species in mine tailings of abandoned mines from Korea.

The main objective of the present study is to determine arsenic species in mine tailings by applying an ion exchange method. Three abandoned mines, Jingok, Cheonbo and Sino mines in Korea, which had produced mainly gold, were selected for the collection and analysis of the tailings. It was found that the arsenic speciation using an ion exchange method was effective to separate As(III) and As(V) in leachate of mine tailings. The concentration of As(V) was found to be 63-99% in the leachate, indicating that As(V) would be the major arsenic species in the mine tailings and the tailings were under oxic conditions. The total concentrations of arsenic and metal elements in the mine tailings were up to 62,350 mg/kg As, 40 wt.% Fe, 21,400 mg/kg Mn, and 7,850 mg/kg Al. Sulfate was the dominant anion throughout the leachate, reaching a maximum dissolved concentration of 734 mg/l. The results of XRD and SEM in the mine tailings showed that main arsenic-containing minerals were pyrite (FeS2) and arsenopyrite (FeAsS) which would be the source of arsenic contamination in the study area.

Adsorption↗

Extraction of lead, cadmium and zinc from overglaze decorations on ceramic dinnerware by acidic and basic food substances.

Dinnerware decorated with overglaze designs can release toxic metals into food substances in amounts high enough to constitute health hazards. When dishes made in the US before 1970 were filled with 4% acetic acid for 24 h, lead concentrations of up to 610 micrograms/ml and cadmium concentrations of up to 15 micrograms/ml were measured. Acetic acid leachates from more than half the dishes tested for lead (78 of 149) contained levels exceeding the US Food and Drug Administration (FDA) allowable concentration of 3.0 micrograms/ml. One-fourth of dishes tested for cadmium (26 of 98) exceeded the FDA limit of 0.5 microgram/ml. High concentrations of lead, cadmium and zinc were also released into 1% solutions of citric and lactic acids. Significant amounts of these metals were extracted by basic solutions of sodium citrate and sodium tripolyphosphate, as well as by commercial food substances including sauerkraut juice, pickle juice, orange juice, and low-lactose milk. Relative concentrations of lead, zinc and cadmium released depend on the leaching agent used. Citric acid leachates contain higher lead:cadmium and zinc:cadmium (but lower lead:zinc) ratios than do acetic acid leachates from nominally identical dishes. Repeated extractions with acetic acid show that even after 20 consecutive 24-h leachings many dishes still release lead in concentrations exceeding FDA limits.

Acetic Acid↗

Leachability of elements from sub-bituminous coal fly ash from India.

Environmental concerns regarding the potential contamination of soil, surface and ground water due to the presence of soluble metal species in the ash pond leachate is of great importance. Serial batch leaching was carried out simulating the rainwater condition of the study area to understand the behaviour of elements during leaching. The leachates were analysed for the elements Al, Ca, K, Mg, Na, P, S, Si, As, Ba, Fe, Mn, Mo, Ti, V, Pb, Zn, Co, Cr, Cu, Ni and Cd by inductively coupled plasma optical emission spectrometer (ICP-OES). It was found that Cd, Co, Cr and Ni did not leach from the ash while Cu and Pb concentrations were insignificant in the leachate regardless of liquid to solid (L/S) ratio. Most of the elements showed maximum concentrations at lower L/S ratio and then decreased with increasing L/S. The total cumulative concentrations of As, Mn and Mo were found to be higher than the World Health Organization (WHO) recommended values for drinking water while the concentrations of Fe, Mn and As exceeded the maximum allowable concentrations prescribed by the United States Environmental Protection Agency (USEPA). The pre and the post leached ash samples were analysed for morphology, specific surface area and mineralogical changes. Analysis of post-leached fly ash indicated changes in the specific surface area and morphology but no change in mineralogy.

Coal↗

Intrinsic degradation of volatile fatty acids in laboratory-compacted clayey soil.

Volatile fatty acids (VFAs) represent the major organic constituent of landfill leachate and provide the greatest potential for leachate induced organic contamination of groundwater (e.g. as represented by an increase in the concentration of dissolved organic carbon and chemical oxygen demand). Long-term diffusion tests were performed for laboratory-compacted clayey soil plugs exposed to continuous supply of synthetic leachate containing VFAs. Significant microbial activity developed upon exposure of the soil's indigenous microorganisms to these degradable contaminants. The growth of heterotrophic aerobic bacteria (HAB, which include facultative anaerobes), sulfate reducing bacteria (SRB) and methanogenic bacteria carrying out fermentation and mineralization of the VFAs became evident after 30-50 days of testing. The maximum microbial counts of (2-8) x 10(8) and (0.1-1) x 10(8) cfu/g for HAB and SRB were localized in the soil layer at the interface with the source of organic and inorganic nutrients. Regardless of this rapid growth in microbial population, the VFA consumption was small and measurable only after a lag of 140-180 days. It is considered that this lag of otherwise readily degradable organic compounds (such as VFAs) persisted due to a combination of the effects of a high initial concentration of these acids (2.4 g/l as dissolved organic carbon, DOC) applied to carbon starved soil microorganisms and the small pore size of the compacted clay. Once the significant amounts of gas were generated from fermentation, conditions developed for improved mass transport and exchange of the nutrients and bacteria and the outcome of the intrinsic degradation was more apparent. The breakdown of VFAs that followed after the lag was localized near the top of the soil and was characterized by a short half-life of 0.75-5 days for DOC (total VFAs as dissolved organic carbon).

Aluminum Silicates↗

Observation and characterization of colloids derived from leached cement hydrates.

The possibility of colloid generation from cement hydrates in a cementitious repository environment has been investigated through leaching experiments. Pulverized samples of High Flyash and Silica fume-content Cement (HFSC) and 1:9 ordinary portland cement/blast furnace slag (1:9 OPC/BFS) hydrate were leached in low-salinity groundwater at three solid-to-liquid (S/L) mass ratios (1:5, 1:50 and 1:100), and two temperatures (20 and 60 degrees C) for durations of nearly 2 and 8 months. Detailed characterization of colloid populations has been undertaken by TEM coupled with X-ray analysis. In addition, the surface charge and stability behavior of colloids have been investigated. The colloid concentrations in HFSC hydrate leachates generated at 20 and 60 degrees C show similar trends with S/L ratio. The colloid concentrations of leachates with the lower S/L ratio (1:50 and 1:100) are in the range of 10(11)-10(12) particles per liter. The majority of these particles are composed predominantly of Si, Ca, and Al; the mean particle size is less than 100 nm. The lowest colloid concentrations are found in the leachates with the highest S/L ratios, and the colloid populations tend to be dominated by larger particles. HFSC-derived colloid stability is due to a high negative zeta potential at alkaline pH values, combined with a calcium concentration that is below the critical coagulation concentration (CCC) for the colloids. A preliminary interpretation of HFSC-derived colloid stability based on classical DLVO theory provides a semi-quantitative explanation of the dependence of colloid populations on the S/L ratio in the leaching experiments.

Colloids↗

Toxic effect of sulfur compounds on anaerobic biogranule.

The effects of sulfide, sulfite and sulfate on degradation of volatile fatty acid (VFA) in UASB process have been studied by using serum bottle assay and septage-leachate acclimated biogranules. The relative toxicity of the compounds towards methane production and degradation of total VFA varied as SO(4)(2-) -S>S(2-)>SO(3)(2-) -S and SO(4)(2-) -S>SO(3)(2-) -S>S(2-), respectively. The difference of this order shows the importance of choosing monitoring factor in evaluating the effect of sulfur compounds on a UASB system. For the individual VFA the effects of sulfur compounds depended on the types of VFA. The VFA-degrading activity of anaerobic biogranules was decreased by 50% when 34, 26 and 20mg of S(2-), SO(3)(2-) -S and SO(4)(2-) -S were added to each gram of biomass, respectively. A comparison of the toxicity-resistance between two different anaerobic biogranules that acclimatized with septage-leachate mixture and septage was also made. In the presence of the leachate, the toxicity-resistance of biogranules was not weakened to sulfide and sulfate but was enhanced to sulfite.

Bacteria, Anaerobic↗

On-site treatment and landfilling of MSWI air pollution control residues.

Air pollution control (APC) residues from municipal solid waste incineration (MSWI) are difficult to landfill due to substantial leaching of trace metals. An on-site pretreatment prior to landfilling of APC-residues was investigated in terms of bench-scale experiments with a semidry APC-residue and a fly ash. The treatment involved mixing of the residues with a ferrous sulphate solution and subsequent oxidation of the suspension. Afterwards, the suspension was spread on a dedicated landfill section and allowed to drain by gravity through the drainage system of the landfill. The wastewater from the process, collected through the drainage system, contained large concentrations of salts (Cl: 14-30 g/l, Na: 4-9 g/l, K: 5-11 g/l, Ca: 2-12 g/l) but low concentrations of trace metals (e.g. Pb: 14-100 microg/l, Cd: <2-7 microg/l). The treated residues left in the landfills were later subject to leaching by simulated rainfall. The leachate contained low concentrations of trace metals (Pb: <120 microg/l, Cd: <2 microg/l, Cr: <485 microg/l). The leachate concentrations from the treated APC-residues were substantially reduced compared to concentrations in leachate from untreated APC-residues. Particularly in the early stages of the leaching, concentrations of trace metals were reduced by up to four orders of magnitude.

Air Pollution↗

Evaluating the applicability of a modified toxicity characteristic leaching procedure (TCLP) for the classification of cementitious wastes containing lead and cadmium.

Having the toxicity characteristic leaching procedure (TCLP) as a starting point, this study examined the effect of the various leaching parameters on the leaching of Pb and Cd from cementitious wastes. Using modified TCLP procedures, the parameters investigated were the acid concentration, leaching duration, particle size of the crushed waste, liquid to solid ratio, and the acid type. The main finding was that the final leachate pH controls the leachability of metals due to its influence on their solubility. The high alkalinity of cementitious waste buffers the leachate at a pH where most metals become insoluble. The TCLP was found to result in an unrealistic condition for cementitious wastes due to the high resultant leachate pH.

Cadmium↗

Energy recovery from grass using two-phase anaerobic digestion.

Municipal solid wastes are major sources of air, water and soil contamination. There is a need for alternative waste management techniques to better utilize the waste and minimize its adverse environmental impact. A two-phase pilot-scale bio-fermentation system was used to evaluate the feasibility of producing methane from grass waste, a major constituent of solid wastes. The bi-phasic system consists of a solid phase and a methane phase. Leachate is re-circulated through the solid phase until a desired level of volatile fatty acid (VFA) is accumulated in the leachate. The leachate is then transferred to the methane reactor where the VFA is converted to methane. The results showed that 67% of the volatile solids in the waste can be converted into soluble chemical oxygen demand in a period of six months. The system produced an average of 0.15 m3 of methane per kg of grass. The average methane concentration in the produced gas was 71%. A mathematical model was developed to estimate the methane and carbon dioxide concentrations in the gas phase as a function of reactor properties.

Biodegradation, Environmental↗

An ecotoxic risk assessment of residue materials produced by the plasma pyrolysis/vitrification (PP/V) process.

Plasma is the fourth state of matter, following the three states of solid, liquid and gas. Experience has amply demonstrated that solids exposed to the oxygen-deficient plasma flame are converted to liquid, and liquid exposed to the same flame is converted to gas. A low amount of vitrified solid residue material usually remains at the end of this process. Plasma pyrolysis/vitrification (PP/V) has been demonstrated as a safe, efficient, cost-effective technology for the treatment of wastes, including hazardous wastes. Besides the low amounts of gaseous byproducts that PP/V produces, the solid vitrified residue presents a low leachability of pollutants. Studies have been performed in many countries in order to assess the leachability of chemical substances. But from the results of identified studies, none has reported results on the ecotoxicological properties of the leachates. The aim of this study was to contribute to the assessment of ecotoxic risk of four different vitrified materials. Vitrified samples of contaminated soils, municipal solid wastes, and incinerator bottom ashes were submitted to the European leaching pre-standard test number prEN 12457-2. The leachates were analyzed for 22 chemical parameters. The biological characterization comprised the assessment of bioluminescence inhibition of Photobacterium phosphoreum bacterium, growth inhibition of Pseudokirchneriella subcapitata algae and the germination inhibition of Lactuca sativa vegetable. The chemical and ecotoxicological results were analyzed according to the French proposal of Criteria on the Evaluation Methods of Waste Toxicity (CEMWT) and a Toxicity Classification System (TCS). The chemical and ecotoxicological results indicated a low leachability of pollutants and a low toxicity level of leachates. All samples studied were as below the TCS class 1 level (no significant toxicity observed) and as non-ecotoxic for CEMWT. Therefore, the environmental ecotoxic risk of the analyzed vitrified samples was determined to be very low.

Chemical Phenomena↗

A comparison of refuse attenuation in laboratory and field scale lysimeters.

For this study, small and middle scale laboratory lysimeters, and a large scale field lysimeter in situ in Shanghai Refuse Landfill, with refuse weights of 187,600 and 10,800,000 kg, respectively, were created. These lysimeters are compared in terms of leachate quality (pH, concentrations of COD, BOD and NH3-N), refuse composition (biodegradable matter and volatile solid) and surface settlement for a monitoring period of 0-300 days. The objectives of this study were to explore both the similarities and disparities between laboratory and field scale lysimeters, and to compare degradation behaviors of refuse at the intensive reaction phase in the different scale lysimeters. Quantitative relationships of leachate quality and refuse composition with placement time show that degradation behaviors of refuse seem to depend heavily on the scales of the lysimeters and the parameters of concern, especially in the starting period of 0-6 months. However, some similarities exist between laboratory and field lysimeters after 4-6 months of placement because COD and BOD concentrations in leachate in the field lysimeter decrease regularly in a parallel pattern with those in the laboratory lysimeters. NH3-N, volatile solid (VS) and biodegradable matter (BDM) also gradually decrease in parallel in this intensive reaction phase for all scale lysimeters as refuse ages. Though the concrete data are different among the different scale lysimeters, it may be considered that laboratory lysimeters with sufficient scale are basically applicable for a rough simulation of a real landfill, especially for illustrating the degradation pattern and mechanism. Settlement of refuse surface is roughly proportional to the initial refuse height.

Biodegradation, Environmental↗

Transformation of phthalates in young landfill cells.

Phthalic acid diesters are additives in a variety of materials that can end up in landfills. Leachates from a series of full-scale young landfill cells were analysed over time for dimethyl, diethyl, dibutyl, butylbenzyl, and di(2-ethylhexyl) phthalate (respectively designated DMP, DEP, DBP, BBP, and DEHP), and their corresponding monoesters monomethyl, monoethyl, monobutyl, monobenzyl, and mono(2-ethylhexyl) phthalate (MMP, MEP, MbutP, MbenzP, and MEHP, respectively), as well as o-phthalic acid (PA). One landfill cell was created in each of three consecutive years by deposition of the same type of waste in July and August. The pH, volatile fatty acids (VFAs), and total organic carbon (TOC) were measured to characterise development of the degradation phases in three landfill cells, which revealed early acidogenic to initial methanogenic stages. Analysis of the phthalate compounds showed that observed concentrations of the degradation products were below the detection limit in the acidogenic leachates but exceeded concentrations of their corresponding diesters in leachates from cells in the initial methanogenic phase. Maximum and average concentrations of phthalic acid were 50 and 23 mg/l, respectively, and the corresponding values for the other phthalates were 430 and 27 microg/l. The concentrations of all phthalates decreased during the establishment of stable methanogenic conditions.

Environmental Monitoring↗

Effect of heavy metals on the growth of a methanogen in pure culture and coculture with a sulfate-reducing bacterium.

The sensitivity of a methanogen and sulfate-reducing bacterium isolated from a sea-based landfill site to Cd2+ and Cu2+ was studied. Methanogens and sulfate-reducing bacteria in leachates of the waste disposal site were enumerated using the MPN method. Methanobacterium thermoautotrophicum KHT-2, isolated from the leachate, could not grow at 0.5 mM Cd2+ or 1.0 mM Cu2+. Desulfotomaculum sp. RHT-3, isolated from the same leachate, was able to insolubilize 3.0 mM Cd2+ or 2.0 mM Cu2+ by production of hydrogen sulfide. When strains KHT-2 and RHT-3 were cultured together in the presence of the heavy metals, strain KHT-2 could grow at high heavy metal concentrations after insolubilization of the metals by strain RHT-3.

Journal Article↗

Critical evaluation of factors required to terminate the postclosure monitoring period at solid waste landfills.

Regulations governing the disposal of solid waste in landfills specify that they must be monitored for 30 years after closure unless this period is extended by the governing regulatory authority. Given the wide range of conditions under which refuse is buried, technical criteria, rather than a specific time period, are preferable for evaluation of when it is acceptable to terminate postclosure monitoring. The objectives of this paper are to identify and evaluate parameters that can be used to define the end of the postclosure monitoring period and to present a conceptual framework for an investigation of whether postclosure monitoring can be terminated at a landfill. Parameters evaluated include leachate composition and leachate and gas production. Estimates of leachate production from closed landfills are used to assess the potential environmental impacts of a hypothetical release to surface water or groundwater. The acceptability of gaseous releases should be evaluated against criteria for odors, the potential for subsurface migration, and greenhouse gas and ozone precursor emissions. The approach presented here must be tested on a site-specific basis to identify additional data requirements and regulatory activity that might be required to prepare regulators for the large number of requests to terminate postclosure monitoring expected over the next 20 years. An approach in which the frequency and extent of postclosure monitoring is reduced as warranted by site-specific data and impact analysis should provide an effective strategy to manage closed landfills.

Environmental Monitoring↗

Sources of sulfate supporting anaerobic metabolism in a contaminated aquifer.

Field and laboratory techniques were used to identify the biogeochemical factors affecting sulfate reduction in a shallow, unconsolidated alluvial aquifer contaminated with landfill leachate. Depth profiles of 35S-sulfate reduction rates in aquifer sediments were positively correlated with the concentration of dissolved sulfate. Manipulation of the sulfate concentration in samples revealed a Michaelis-Menten-like relationship with an apparent Km and Vmax of approximately 80 and 0.83 microM SO4(-2) x day(-1), respectively. The concentration of sulfate in the core of the leachate plume was well below 20 microM and coincided with very low reduction rates. Thus, the concentration and availability of this anion could limit in situ sulfate-reducing activity. Three sulfate sources were identified, including iron sulfide oxidation, barite dissolution, and advective flux of sulfate. The relative importance of these sources varied with depth in the alluvium. The relatively high concentration of dissolved sulfate at the water table is attributed to the microbial oxidation of iron sulfides in response to fluctuations of the water table. At intermediate depths, barite dissolves in undersaturated pore water containing relatively high concentrations of dissolved barium (approximately 100 microM) and low concentrations of sulfate. Dissolution is consistent with the surface texture of detrital barite grains in contact with leachate. Laboratory incubations of unamended and barite-amended aquifer slurries supported the field observation of increasing concentrations of barium in solution when sulfate reached low levels. At a deeper highly permeable interval just above the confining bottom layer of the aquifer, sulfate reduction rates were markedly higher than rates at intermediate depths. Sulfate is supplied to this deeper zone by advection of uncontaminated groundwater beneath the landfill. The measured rates of sulfate reduction in the aquifer also correlated with the abundance of accumulated iron sulfide in this zone. This suggests that the current and past distributions of sulfate-reducing activity are similar and that the supply of sulfate has been sustained at these sites.

Bacteria, Anaerobic↗

Effect of remineralization on heavy-metal leaching from cement-stabilized/solidified waste.

Crushed samples of stabilized/solidified (s/s) waste were leached at constant leachate pH in the pH range 4-7 with nitric acid solutions to evaluate the influence of remineralization on metal release. The s/s waste consisted of synthetic heavy-metal sludge containing 0.1 mol L(-1) copper nitrate, 0.1 mol L(-1) zinc nitrate, and 0.1 mol L(-1) lead nitrate mixed with ordinary Portland cement. Unleached and leached particles were characterized by scanning electron microscopy and energy-dispersive X-ray spectrometry. Two consecutive leaching fronts advancing from the surface of the particles toward the center were identified: the first front was associated with the dissolution of portlandite and partial reaction of the calcium silicate hydrate gel, while the second front was associated with the dissolution of calcium-aluminum hydroxy sulfates such as ettringite and monosulfate. At pH 4 and 5, a remineralization zone rich in heavy metals formed immediately behind the second leaching front. The shell extending from the remineralization zone to the surface of the particles was depleted in calcium, sulfate, and heavy metals. As a result of remineralization, heavy-metal releases to the leachate were reduced by factors ranging between 3.2 and 6.2 at pH 4 and between 74 and 193 at pH 5. At pH 6 and 7, remineralization of Pb and Zn occurred further behind the second leaching front and closer to the surface of the particles. The amount of heavy-metal release depended on both the leachate pH and the remineralization factor.

Construction Materials↗

Ecotoxicity assessment of stabilized/solidified foundry sludge.

The aim of this study is to evaluate the toxicity of the leachates from a foundry sludge and the derived products based on the stabilization/solidification (S/S) processes. Foundry sludge is an industrial hazardous waste containing inorganic and organic pollutants. The immobilization of the foundry waste has been performed using different S/S procedures based on cement or lime as binder agents and foundry sand fines, calcium-magnesium lignosulfonate, silica fume, activated carbon and black carbon as additives. The waste and stabilized/solidified derived products have been evaluated according to environmental considerations. The relation between the chemical composition and the ecotoxicity of the leachates has been studied in this paper. The ecotoxicity of the leachates has been related to the heavy metals and the organic pollutants by an empirical logarithmic linear expression. Different parameters of the logarithmic fitting have been obtained for the studied binder agents and additives allowing the establishment of a relationship between the S/S process and the ecotoxicity of the derived products. Results of this study have wide-ranging implications for immediate management strategies of waste with organic and inorganic pollutants in addition to application in long-term remediation efforts.

Carbon↗