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Anaerobic methane oxidation in a landfill-leachate plume.

The alluvial aquifer adjacent to Norman Landfill, OK, provides an excellent natural laboratory for the study of anaerobic processes impacting landfill-leachate contaminated aquifers. We collected groundwaters from a transect of seven multilevel wells ranging in depth from 1.3 to 11 m that were oriented parallel to the flow path. The center of the leachate plume was characterized by (1) high alkalinity and elevated concentrations of total dissolved organic carbon, reduced iron, and methane, and (2) negligible oxygen, nitrate, and sulfate concentrations. Methane concentrations and stable carbon isotope (delta13C) values suggest anaerobic methane oxidation was occurring within the plume and at its margins. Methane delta13C values increased from about -54 per thousand near the source to > -10 per thousand downgradient and at the plume margins. The isotopic fractionation associated with this methane oxidation was -13.6+/-1.0 per thousand. Methane 13C enrichment indicated that 80-90% of the original landfill methane was oxidized over the 210-m transect. First-order rate constants ranged from 0.06 to 0.23 per year, and oxidation rates ranged from 18 to 230 microM/y. Overall, hydrochemical data suggest that a sulfate reducer-methanogen consortium may mediate this methane oxidation. These results demonstrate that natural attenuation through anaerobic methane oxidation can be an important sink for landfill methane in aquifer systems.

Bacteria, Anaerobic↗

Arsenic speciation of solvent-extracted leachate from new and weathered CCA-treated wood.

For the past 60 yr, chromate-copper-arsenate (CCA) has been used to pressure-treat millions of cubic meters of wood in the United States for the construction of many outdoor structures. Leaching of arsenic from these structures is a possible health concern as there exists the potential for soil and groundwater contamination. While previous studies have focused on total arsenic concentrations leaching from CCA-treated wood, information pertaining to the speciation of arsenic leached is limited. Since arsenic toxicity is dependent upon speciation, the objective of this study was to identify and quantify arsenic species leaching from new and weathered CCA-treated wood and CCA-treated wood ash. Solvent-extraction experiments were carried out by subjecting the treated wood and the ash to solvents of varying pH values, solvents defined in the EPA's Synthetic Precipitation Leaching Procedure (SPLP) and Toxicity Characteristic Leaching Procedure (TCLP), rainwater, deionized water, and seawater. The generated leachates were analyzed for inorganic As(III) and As(V) and the organoarsenic species, monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA), using high-performance liquid chromatography followed by hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS). Only the inorganic species were detected in any of the wood leachates; no organoarsenic species were found. Inorganic As(V) was the major detectable species leaching from both new and weathered wood. The weathered wood leached relatively more overall arsenic and was attributed to increased inorganic As(III) leaching. The greater presence of As(III) in the weathered wood samples as compared to the new wood samples may be due to natural chemical and biological transformations during the weathering process. CCA-treated wood ash leached more arsenic than unburned wood using the SPLP and TCLP, and ash samples leached more inorganic As(III) than the unburned counterparts. Increased leaching was due to higher concentrations of arsenic within the ash and to the conversion of some As(V) to As(III) during combustion.

Arsenates↗

Comparison of BOD results obtained by dilution and manometric methods in sanitary landfill leachates.

This study examined the determination of BOD in landfill leachates by dilution (D-method) and manometric methods (M-method). The differences in results were discussed based on statistical tests. The effects of sample dilution, seeding, chloride and total Kjeldahl nitrogen (TKN) level were examined. The M-method was found to be more sensitive to increases in chloride and TKN concentrations. However, in the M-method the positive interference of nitrogenous BOD (NBOD) to carbonaceous BOD (CBOD) was more successfully prevented. The BOD rate constant k and the ultimate BOD (BODu) were estimated by non-linear regression. With the M-method these parameters could be more reliably estimated than the D-method. Suggestions were made for BOD analyses in landfill leachates in future studies.

Biodegradation, Environmental↗

Characterization of landfill leachates and studies on heavy metal removal.

This study covers a thorough characterisation of landfill leachates emerging from a sanitary landfill area. The landfill leachates were obtained in the acidic stage of landfill stabilisation. Their organic content was high as reflected by the high BOD5 (5 day biological oxygen demand) and COD (chemical oxygen demand) values. They were also highly polluted in terms of the parameters TKN (total Kjeldahl nitrogen), NH4-N, alkalinity, hardness and heavy metals. Nickel was present in these wastewaters at a significant concentration. With regard to the high heavy metal content of these wastewaters, several physicochemical removal alternatives for the heavy metals Cu, Pb, Zn, Ni, Cd, Cr, Mn and Fe were tested using coagulation, flocculation, precipitation, base addition and aeration. Additionally, COD removal and ammonia stripping were examined. Co-precipitation with either alum or iron salts did not usually lead to significantly higher heavy metal removal than lime alone. The major methods leading to an effective heavy metal removal were aeration and lime addition. Nickel and cadmium seemed to be strongly complexed and were not removed by any method. Also lead removal proved to be difficult. The results are also discussed in terms of compliance with standards.

Environmental Monitoring↗

Determination of estrogenic activity in landfill leachate by simplified yeast two-hybrid assay.

We previously developed a simplified yeast two-hybrid assay of estrogenic activity. In the present study, the optimal conditions for sensitivity and stability of this assay were decided. The assay could determine the estrogenic activity of 4 x 10(-11) mol dm(-1) 17beta-estradiol and also anti-estrogenic activity by using 4-hydroxytamoxifen as a control. The assay was used to test various chemicals suspected of estrogenicity. Many kinds of chemical, including alkylphenols, naphthols, xylenols, methoxychlor, phthalates, and bisphenol-A, showed estrogenic activity, and several, such as 2,5-xylenol and di-iso-octyl phthalate, showed anti-estrogenic but no estrogenic activity. Copresence of two estrogenic chemicals produced additive activity. The assay was also used to test leachate and water samples from the sea-based landfill of Osaka North Port in Japan. Estrogenic activity was detected in leachate from a municipal waste-dumping site, but not in that from a dredged soil-dumping site, which did however cause inhibition of cell growth.

Biological Assay↗

Influence of recirculation flow rate on the performance of anaerobic packed-bed bioreactors treating potato-waste leachate.

The performance of anaerobic, packed-bed bioreactors treating leachate from potato waste was evaluated in terms of organic loading rate (OLR) as well as the recirculation flow rate. Two 1 litre bioreactors, filled with porous glass beads as biofilm carriers and with continuous recirculation flow rates of 10 ml min(-1) and 20 ml min(-1) respectively, were used in the experiment. The OLR applied to each bioreactor was increased stepwise from 4 to 12 kg chemical oxygen demand (COD) m(-3)d(-1) by increasing feed flow rate. The methane yields decreased with increasing OLR in both bioreactors. The methane yield for the bioreactor with the lower recirculation flow rate ranged between 0.10 and 0.14 m3 CH4 kg COD(-1) removed, while for the other bioreactor it was 0.14-0.20 m3 CH4 kg COD(-1) removed. Both bioreactors demonstrated stable COD removal which was around 95% for the bioreactor with lower flow of recirculation while for the other it was 92%, over a range of OLRs of 4-8 kg COD m(-3)d(-1). The bioreactor with the lower recirculation flow rate showed operational stability when a high OLR, namely 12 kg COD m(-3)d(-1), was applied, while the other one became overloaded. There was an accumulation of volatile fatty acids which gave a corresponding drop in pH because the system had a low buffering capacity and this thus ultimately led to process failure. This study demonstrated the suitability of a packed bed bioreactor operated at lower recirculation flow rate for treating leachate from potato waste.

Agriculture↗

Electrochemical oxidation of leachate pretreated in an upflow anaerobic sludge blanket reactor.

This study was conducted to develop a two-stage process for the treatment of Hong Kong leachate. The leachate, containing 4750 mg l-1 of chemical oxygen demand (COD) and 1310 mg l-1 of ammoniacal nitrogen (NH3-N), was first treated in a UASB (upflow anaerobic sludge blanket) reactor at 37 degrees C. The process removed on average 66.1% of COD with 6.1 days of hydraulic retention time (HRT), corresponding to an organic loading rate of 0.78 g-COD (l.day)-1. The UASB effluent, which had an average pH of 8.9, COD of 1610 mg l-1 and NH3-N of 1480 mg l-1, was then further treated by electrochemical oxidation in a batch reactor with recirculation. With the addition of 2000 mg l-1 of chloride (in the form of sodium chloride) and at a current density of 32.3 mA cm-2, 87% of COD and 100% of NH3-N were removed from the UASB effluent in six hours. The energy consumption was < 55 kWh kg-COD-1. The final effluent contained no residual NH3-N and only 209 mg l-1 of COD.

Electrochemistry↗

A pre- and post-denitrification system treating a very high ammonia landfill leachate: effects of pH change on process performance.

The prime objective of this research was to investigate the nitrogen removal capabilities of a pre- and post-denitrification process, when treating landfill leachate containing an ammonia concentration of over 2,200 mg N l(-1). The treatment system, also known as a 4-Stage Bardenpho process, was operated with an external recycle ratio of 3:1 and an internal recycle ratio of 4:1. The first anoxic reactor actual hydraulic retention time was 1.5 hours, while the first aerobic retention time was 3 hours. The very high ammonia concentration was simulated by pumping ammonium chloride into the first anoxic reactor of the system. Methanol was used as the organic carbon source for denitrification. At an influent ammonia concentration of about 2,200 mg N l(-1), the anoxic pH levels stabilized at about 8.6 within the first reactor, and at about 9.8 within the second reactor. These high anoxic pH levels were partially responsible for decreased denitrification and, hence, residual NO concentrations in the effluent. By decreasing the pH in the anoxic basins, the overall performance of the system immediately improved; the effluent NOx concentration decreased rapidly over a period of about six days, from an average 80 mg N l(-1) to about 60 mg N l(-1), with some samples as low as 40 mg N l(-1). Subsequently, increased leachate toxicity resulted in an unexpected system failure; although the treatment system eventually recovered and stabilized, denitrification in each anoxic reactor remained at only about 55%, with final effluent NOx concentrations of over 100 mg N l(-1). Despite this reduced level of performance, the decrease in anoxic pH resulted in enhanced nitrification performance, complete ammonia removal in the first aerobic reactor, and a more stable, overall performance in the 4-Stage Bardenpho process.

Ammonia↗

A novel design for anaerobic chemical oxygen demand and nitrogen removal from leachate in a semiaerobic landfill.

The removal capacity of carbon and nitrogen from an artificial leachate was evaluated by using laboratory-scale columns, and a design was proposed to remove nitrogen more efficiently from a semiaerobic landfill. Five columns (i.e., two artificial municipal waste columns under anaerobic and semiaerobic conditions, an artificial construction waste column under semiaerobic conditions, and two crushed stone columns under anaerobic and semiaerobic conditions) were used. The influent load rates of organics [g chemical oxygen demand (COD)/m3 x day], NH4+, NO3- and aeration conditions for the columns were varied, and the removal capacities of the columns for COD, NH4+-N, and NO3--N were measured. Among the packed column materials, crushed stone was shown to be most effective in removing COD, NH4+ N, and NO3--N from artificial leachate. Average removal rates of crushed column under the semiaerobic condition (column D) for COD and NH4+-N were estimated at about 150 g COD/m3 x day and 20 g COD/m3 x day, while those of crushed column under anaerobic condition (column E) for COD and NO3--N at about 400 and 150 g COD/m3 x day, respectively. It also was found that denitrification and nitrification reactions in column D occurred at the same time, and the ratio of denitrification to nitrification was estimated to be about 80%. Therefore, an anaerobic structure, which could be attached to the bottom of a main pipe in a semiaerobic landfill, is suggested to remove nitrogen and organic substances more effectively.

Bacteria, Anaerobic↗

A comparative study of sulfidogenic and methanogenic activities during the treatment of landfill leachate: part I.

A comprehensive anaerobic leachate treatment in batch reactors was conducted for 9 months. Activities of two main bacterial groups, sulfidogens and methanogens were observed with monitoring parameters as chemical oxygen demand (COD), total gas production, pH, alkalinity, dissolved sulfide and volatile suspended solids/total suspended solids (VSS/TSS). Leachate contained high concentrations of volatile fatty acids. Some competition between microbial species was observed. COD was applied at a range of 1100-8200 mg/L at a slowly increasing rate over time. COD removal was mostly above 80%, dissolved sulfide was produced at a range of 100-450 mg/L in the first weeks, proving high sulfidogenic activity and making 40-50% of COD removal. Methanogenesis seemed under stress and improved after several weeks with increasing COD load whereas hydrogen sulfide (HS-) production leveled off around 100 mg/L, making 4-8% COD removal by sulfidogens. Then, 40-70% of overall COD removal was achieved by methanogens. Volatile fatty acids (VFA) except acetic acid (propionic, isobutyric, butyric, isovaleric, valeric, caproic and heptanoic acids) were readily degraded and found near detection limit on gas chromatographic runs, accordingly VFA-oxidizing bacteria were assumed to be highly active and tolerant to sulfide levels encountered in our study, also with hydrogenotrophic groups providing favorable conditions for the process. pH was the key parameter to determine the degree of inhibition from sulfurous species. Alkalinity was produced proportionally with COD applied as a result of VFA degradation. Overall system performance was good and optimum pH was 7.8-8.2 at which inhibition due to unionized VFA was eliminated.

Anaerobiosis↗

Treatment of landfill leachate with aerated and non-aerated submerged biofilters.

A submerged biological filter packed with clayey schists from brick industrial waste as support material was used to treat landfill leachate. The pilot-scale plant consisted of two separated reactors, running in aerated and non-aerated conditions respectively. The leachate was taken from a landfill in Granada (southeast Spain) and was considered as partially stabilized with average chemical oxygen demand (COD) concentrations of 18,683.3 mg COD/L. The efficiency of the system at reducing COD, biological oxygen demand (BOD(5)), total suspended solids (TSS), total volatile solids (TVS), total solids (TS), cations and anions concentrations was tested comparing aerating and non-aerating conditions under several volumic organic loadings (15.7, 25.1 and 31.1 kg COD/m(3)d), a hydraulic loading of 0.7 m(3)/m(2)d and an internal recirculation of 250%. Results obtained showed that the aerated reactor was more effective than the non-aerated reactor in the removal of COD, BOD5 and TS, with maximum efficiencies of 66.7%, 91.2% and 21.7%, respectively. The volumic organic loading of 25.1 COD/m(3)d obtained best results. However, for the removal of TSS and TVS the non-aerated reactor showed better results (42%). The behaviour of different cations (Na(+), K(+), and Mg(2+)) and anions (F(-), Cl(-), Br(-)) was also monitored and a reduction in their concentration in the effluent was detected, in the order of 61% for Ca(2+) and 100% for F(-).

Air Movements↗

Inhibition of lymphocyte blastogenesis by serum leachates of fly ash.

Samples of 8 ashes were leached with canine serum for 24 h to remove metal ions from the particle surfaces. The particles were removed by filtration, and the concentrations of 11 metal ions in the serum leachates were determined by atomic absorption spectrophotometry. The leachate samples were evaluated using the canine whole-blood lymphocyte stimulation test (WB/LST). The serum extracts of oil-related ashes were highly inhibitory, while lower biological activity was observed for the extracts of coal ashes. The observed inhibition in the WB/LST was correlated with the concentration of each metal ion using Kendall's rank correlation test. The highest correlations were observed for Mn and V. The results are compared with previous WB/LST studies on pure metal salts.

Aerosols↗

Modification of coagulation and Fenton oxidation processes for cost-effective leachate treatment.

Physicochemical processes have been used to remove nonbiodegradable organic compounds in leachate generated from sanitary landfills. In this study, a coagulation process combined with Fenton oxidation was evaluated for the removal of refractory organics in leachate. Recycling of sludge generated from Fenton oxidation to a coagulation process was attempted to reduce operation cost and to improve organic removal rate. The addition mode of Fenton reagent was also modified to obtain a better organic removal rate and more cost-effective operation. With Fenton sludge recycling, 9% higher COD removal was obtained, and the sludge to be disposed could be reduced up to 50%. Also, the coagulant could be reduced by 50%. For Fenton oxidation process, stepwise addition of reagents gave a 5% higher COD removal, and a 25% reduction in chemical consumption.

Cost-Benefit Analysis↗

Ammonia removal from compost leachate using zeolite. III. Regeneration of zeolite columns.

The effects of hydraulic reteneration time (HRT), and the strength of the regenerating solution on the ammonia adsorption capacity and the zeolite regeneration were studied using bench-scale packed zeolite columns. A 0.6 M NaCl solution fed at a HRT of I h was preferred for the regeneration process, and more than 95% of adsorbed ammonium ions were recovered after using 7-8 bed volumes (BV) of the regenerating solution. The adsorption-regeneration time ratio was approximately 5:1. High concentration of potassium ions in the composting leachate competed with NH4+ ions for the exchange sites, resulting in a reduction in the efficiencies of ammonia removal and zeolite column regeneration. However, Zeolite still proved to have a great potential as a medium for ammonia removal in treating composting leachate.

Adsorption↗

Nitrogen removal in leachate using carrousel activated sludge treatment process.

This paper presents the application of Carrousel Activated Sludge Treatment Process (CASTP) for ammonium nitrogen removal. High concentrations of ammonium nitrogen were found in landfill leachate. When leachate is treated in a local wastewater treatment plant, it has the potential to disturb the operations in the wastewater treatment plant. Because of the advantages of Carrousel Activated Sludge Treatment Process, several pilot studies and kinetic reactions of ammonium nitrogen removal in the CASTP were studied. High circulation and low dissolved oxygen in the CASTP enhances nitrification and denitrification processes. The results indicated that approximately 50-85% ammonium nitrogen and nitrate nitrogen were removed by using a conventional CASTP process. Two key parameters in the CASTP were further studied. The system detention time (SDT) appeared more important than the sludge retention time (SRT) in the CASTP. According to the experimental data, 24 h of the system detention time and 25 days of the sludge retention time achieved 85% or more ammonium nitrogen removal.

Equipment Design↗

Investigation of the effect of free ammonia concentration upon leachate treatment by shortcut biological nitrogen removal process.

A shortcut biological nitrogen removal (SBNR) process was operated to treat an ammonium rich landfill leachate using a pilot-scale reactor. The SBNR process was intended to oxidize ammonia to nitrite and, then, to reduce it to nitrogen gas. When the hydraulic retention time was 4-3 days, a half of the ammonium oxidized was accumulated as nitrite in the oxidation tank. The nitrite was denitrified completely in the anoxic tank when recycled. The average free ammonia (FA) concentration in the ammonium oxidation tank was 3.7 mg/L. The specific substrate utilization rates of ammonium oxidizers and nitrite oxidizers were investigated at varying FA concentrations through batch experiments. The highest specific ammonium oxidation rate was observed when the FA concentration was 10 mg/L. The rate decreased slightly when the FA concentration was increased to 20 or 50 mg/L, or decreased significantly when it was 5 mg/L. In case of nitrite oxidation, the specific nitrite utilization rate decreased significantly with increasing FA concentration up to 10 mg/L. Consequently, the optimal FA concentration in leachate treatment was 10 mg/L for maximum nitrite accumulation and maximum ammonium removal, or 5 mg/L for lower ammonium concentration and reasonable nitrite accumulation.

Bioreactors↗

Toxicity identification of poultry litter aqueous leachate.

Poultry litter is a mixture of excreta, feed, feathers, and bedding material. Poultry litter is useful as a fertilizer due to the presence of nitrogen, phosphorus, and potassium. Litter is commonly used for growing corn, soybeans, potatoes, tomatoes, leafy vegetables, and cover crops. The aqueous leachate of poultry litter has been shown to exhibit toxicity to a variety of indicator organisms. The objective of this research was to identify classes of toxicants in the litter aqueous leachate. The aqueous extract of poultry litter was subjected to toxicity identification tests approved by the United States Environmental Protection Agency that use Ceriodaphnia dubia as the test organism. Tests performed included pH adjustment, filtration, aeration, C18 solid-phase extraction, EDTA addition, sodium thiosulfate addition, and extraction through zeolite. Zeolite extraction, filtration at low pH, and aeration at low pH reduced overall toxicity by 68, 20, and 22%, respectively. The major sources of toxicity appear to be ammonia and anionic organic compounds. Toxicity was apparently not due to the presence of heavy metals or oxidants.

Ammonia↗

Diversity and structure of the archaeal community in the leachate of a full-scale recirculating landfill as examined by direct 16S rRNA gene sequence retrieval.

The diversity and structure of the archaeal community in the effluent leachate from a full-scale recirculating landfill was characterized by direct 16S rRNA gene (16S rDNA) retrieval. Total-community DNA was extracted from the microbial assemblages in the landfill leachate, and archaeal 16S rDNAs were amplified with a universally conserved primer and an Archaea-specific primer. The amplification product was then used to construct a 16S rDNA clone library, and 70 randomly selected archaeal clones in the library were grouped by restriction fragment length polymorphism (RFLP) analysis. Sequencing and phylogenetic analysis of representatives from each unique RFLP type showed that the archaeal library was dominated by methanogen-like rDNAs. Represented in the kingdom of Euryarchaeota were phylotypes highly similar to the methanogenic genera Methanoculleus, Methanosarcina, Methanocorpusculum, Methanospirillum and Methanogenium, where the clone distribution was 48, 11, 3, 1 and 1, respectively. No sequences related to known Methanosaeta spp. were retrieved. Four rDNA clones were not affiliated with the known methanogenic Archaea, but instead, they were clustered with the uncultured archaeal sequences recently recovered from anaerobic habitats. Two chimeric sequences were identified among the clones analyzed.

Archaea↗