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).     

Influence of ultrasonication on anaerobic bioconversion of sludge.

The influence of ultrasonication on hydrolysis, acidogenesis, and methanogenesis in anaerobic decomposition of sludge was investigated. The sonicated sludge exhibited prehydrolysis and preacidogenesis effects in the anaerobic decomposition process. First-order hydrolysis rates increased from 0.0384 day(-1) in the control digester to 0.0672 day(-1) in the digester fed, with sludge sonicated at 0.52 W/mL. The sonication appeared to be ineffective in relation to acidogenesis reaction rates, but it provided a better buffering capacity to diminish the adverse effect of acidification. Digesters fed with sonicated sludge demonstrated enhanced methanogenesis over the control unit. Determination by coenzyme F420 verified that sonication is able to promote the growth of methanogenic biomass and facilitate a positive methanogenic microbial development in suppressing the initial methanogenesis limitation. The results suggest that ultrasonication could enhance anaerobic decomposition of sludge, resulting in an accelerated bioconversion, improved organics degradation, improved biogas production, and increased methane content.     

Heavy metals mobility in full-scale bioreactor landfill: initial stage

Selected heavy metals (HMs) including Cd, Cr, Cu, Ni, Pb and Zn initially released from a full-scale bioreactor landfill were monitored over the first 20 months of operation. At the initial landfill stage, the leachate exhibited high HMs release, high organic matter content (27000-43000gl(-1) of TOC) and low pH (5-6). By the fifth month of landfilling, the methanogenic stage had been established, and HMs release was reduced below the Chinese National Standards. Total released HMs accounted for less than 1% of landfill deposited during the investigated period. Most landfill HMs were inorganic. Fourier-transform infrared (FT-IR) spectra data and model calculations using Visual MINTEQ indicated that humic substances strongly affected the mobility of organic fractions of HMs in the methanogenic landfill. The initial rates of HMs release could be enhanced by recycling the leachate back to bioreactor landfill, but the total quantity released may be reduced by early establishment of methanogenic stage in bioreactor landfill.     

Attenuation of landfill leachate by UK Triassic sandstone aquifer materials: 2. Sorption and degradation of organic pollutants in laboratory columns

The sorption and degradation of dissolved organic matter (DOM) and 13 organic micropollutants (BTEX, aromatic hydrocarbons, chloro-aromatic and -aliphatic compounds, and pesticides) in acetogenic and methanogenic landfill leachate was studied in laboratory columns containing Triassic sandstone aquifer materials from the English Midlands. Solute sorption and degradation relationships were evaluated using a simple transport model. Relative to predictions, micropollutant sorption was decreased up to eightfold in acetogenic leachate, but increased up to sixfold in methanogenic leachate. This behaviour reflects a combination of interactions between the micropollutants, leachate DOM and aquifer mineral fraction. Sorption of DOM was not significant. Degradation of organic fractions occurred under Mn-reducing and SO₄-reducing conditions. Degradation of some micropollutants occurred exclusively under Mn-reducing conditions. DOM and benzene were not significantly degraded under the conditions and time span (up to 280 days) of the experiments. Most micropollutants were degraded immediately or after a lag phase (32–115 days). Micropollutant degradation rates varied considerably (half-lives of 8 to >2000 days) for the same compounds (e.g., TeCE) in different experiments, and for compounds (e.g., naphthalene, DCB and TeCA) within the same experiment. Degradation of many micropollutants was both simultaneous and sequential, and inhibited by the utilisation of different substrates. This mechanism, in combination with lag phases, controls micropollutant degradation potential in these systems more than the degradation rate. These aquifer materials have a potentially large capacity for in situ bioremediation of organic pollutants in landfill leachate and significant degradation may occur in the Mn-reducing zones of leachate plumes. However, degradation of organic pollutants in acetogenic leachate may be limited in aquifers with low pH buffering capacity and reducible Mn oxides. Contaminants in this leachate present a greater risk to groundwater resources in these aquifers than methanogenic leachate.     

光电芬顿氧化法深度处理垃圾渗滤液研究

采用光电芬顿氧化法对北京市某垃圾填埋场已经生化处理后的垃圾渗滤液进行深度处理，分别考察了电流强度和铁的不同价态等因素对渗滤液总有机碳（TOC）、化学需氧量（COD）以及色度去除效果的影响，并对阳极氧化、电芬顿和光电芬顿不同反应过程进行了对比。通过分析渗滤液UV-Vis光谱(200～500 nm)变化和渗滤液中有机污染物的分子量变化，发现光电芬顿反应可以明显改善渗滤液生化性。深入研究了反应过程中铁价态的变化规律。试验结果发现，以高比表面积的活性炭纤维(ACF)为阴极的光电芬顿反应可以有效降解垃圾渗滤液，在pH为3，Fe²⁺ 浓度为1 mmol/L，电流为0.5 A，O₂通入量为250 mL/min条件下降解360 min，垃圾渗滤液TOC和COD去除率分别达到78.9%和62.8%，色度完全去除。     

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.     

Influence of soil organic matter on the leaching of polycyclic aromatic hydrocarbons in soil

Polycyclic aromatic hydrocarbons (PAHs) are one of the main classes of contaminants in the terrestrial environment. Aside from total organic carbon, the ratio among the different organic matter fractions [dissolved organic matter, fulvic acid (FA), humic acid (HA) and humin] can also affect the mobility of these hydrocarbons in soils. In this study the effect of the whole organic carbon pool has been compared with that of HA and FA on the translocation of four PAHs (biphenyl, fluorene, phenanthrene and pyrene) in soil columns. Oxidized and untreated soil columns with and without HA or FA, were prepared, spilled with hydrocarbons and leached with a 0.01 M CaCl2 solution. The influence of HA and FA on PAH translocation was investigated through determinations of the PAH contents and total organic carbon (TOC) in the layers of the columns. All molecules were moved vertically by the percolating solutions, their concentrations decreasing with depths. The nonoxidized soil tended to retain more PAHs (96%) than the oxidized one (60%), confirming that organic matter plays an important role in controlling PAH leaching. The whole organic matter pool reduced the translocation of pollutants downward the profile. The addition of HA enhanced this behaviour by increasing the PAH retention in the top layers (7.55 mg and 4.00 mg in the top two layers, respectively) while FA increased their mobility (only 2.30 and 2.90 mg of PAHs were found in the top layers) and favoured leaching. In fact, in the presence of HA alone, the higher amounts of PAHs retained at the surface and the good correlation (r2=0.936) between TOC and hydrocarbon distribution can be attributed to a parallel distribution of PAHs and HA, while in the presence of FA, the higher mobility of PAHs can be attributed to the high mobility of the humic material, as expected by its extensive hydrophilic characteristics.     

INFLUENCE OF SOIL ORGANIC MATTER ON THE LEACHING OF POLYCYCLIC AROMATIC HYDROCARBONS IN SOIL

Polycyclic aromatic hydrocarbons (PAHs) are one of the main classes of contaminants in the terrestrial environment. Aside from total organic carbon, the ratio among the different organic matter fractions [dissolved organic matter, fulvic acid (FA), humic acid (HA) and humin] can also affect the mobility of these hydrocarbons in soils. In this study the effect of the whole organic carbon pool has been compared with that of HA and FA on the translocation of four PAHs (biphenyl, fluorene, phenanthrene and pyrene) in soil columns. Oxidized and untreated soil columns with and without HA or FA, were prepared, spilled with hydrocarbons and leached with a 0.01 M CaCl₂ solution. The influence of HA and FA on PAH translocation was investigated through determinations of the PAH contents and total organic carbon (TOC) in the layers of the columns. All molecules were moved vertically by the percolating solutions, their concentrations decreasing with depths. The non-oxidized soil tended to retain more PAHs (96%) than the oxidized one (60%), confirming that organic matter plays an important role in controlling PAH leaching. The whole organic matter pool reduced the translocation of pollutants downward the profile. The addition of HA enhanced this behaviour, by increasing the PAH retention in the top layers (7.55 mg and 4.00 mg in the top two layers, respectively) while FA increased their mobility (only 2.30 and 2.90 mg of PAHs were found in the top layers) and favoured leaching. In fact, in the presence of HA alone, the higher amounts of PAHs retained at the surface and the good correlation (r²=0.936) between TOC and hydrocarbon distribution can be attributed to a parallel distribution of PAHs and HA, while in the presence of FA, the higher mobility of PAHs can be attributed to the high mobility of the humic material, as expected by its extensive hydrophilic characteristics.     

Transport of Escherichia coli through variably saturated sand columns and modeling approaches

A sand column leaching system with well-controlled suction and flow rate was built to investigate the effects on bacterial transport of air-water interface effects (AWI) correlated to water content, particle size, and column length. Adsorption of Escherichia coli strain D to silica sands was measured in batch tests. The average % adsorption for coarse and fine sands was 45.9+/-7.8% and 96.9+/-3.2%, respectively. However, results from static batch adsorption experiments have limited applicability to dynamic bacterial transport in columns. The early breakthrough of E. coli relative to bromide was clear for all columns, namely c. 0.15 to 0.3 pore volume earlier. Column length had no significant effects on the E. coli peak concentration or on total recovery in leachate, indicating retention in the top layer of sands. Tailing of breakthrough curves was more prominent for all fine sand columns than their coarse sand counterparts. Bacterial recovery in leachate from coarse and saturated sand columns was significantly higher than from fine and unsaturated columns. Observed data were fitted by the convection-dispersion model, amended for one-site and two-site adsorption to particles, and for air-water interface (AWI) adsorption. Among all models, the two-site+AWI model achieved consistently high model efficiency for all experiments. Thus it is evident from experimental and modeling results that AWI adsorption plays an important role in E. coli transport in sand columns.     

Evolution of clog formation with time in columns permeated with synthetic landfill leachate

Laboratory column tests conducted to gain insight regarding the biological and chemical clogging mechanisms in a porous medium are presented. To seed the porous medium with landfill bacteria, a mixture of Keele Valley Landfill and synthetic leachate permeated through the column under anaerobic conditions for the first 9 days of operation. After this, 100% synthetic leachate was used. The synthetic leachate approximated Keele Valley Landfill leachate in chemical composition but contained negligible suspended solids and bacteria compared with real leachate. The removal of volatile fatty acids (VFAs), primarily acetate, in leachate as it passed through the medium was highly correlated with the precipitation of calcium carbonate (CaCO(3(s))) from solution. The columns experienced a decrease in drainable porosity from an initial value of about 0.38 to less than 0.1 after steady state chemical oxygen demand (COD) removal, resulting in a five-order magnitude decrease in hydraulic conductivity. The decrease in drainable porosity prior to steady state COD removal was primarily due to the growth of a biofilm on the medium surface. After steady state COD removal, calcium precipitation was at least equally responsible for the decrease in drainable porosity as biofilm growth. Clog composition analyses showed that CaCO(3(s)) was the dominant clog constituent and that 99% of the carbonate in the clog material was bound to calcium.     

Biodegradation behavior of agricultural pesticides in anaerobic batch reactors

This study explored the biodegradation potential of two agricultural pesticides (2,4-D and isoproturon) as well as their effect on the performance of the anaerobic digestion process. Three 3.5 L batch reactors were used, having the same initial isoproturon concentration (25 mg/L) and different 2,4-D concentrations (i.e. 0, 100, or 300 mg/L, respectively). All systems were fed with equal amounts of primary sludge and digested sludge and operated at the low mesophilic range (32 ± 2°C). Following an acclimation period of approximately 30 days, complete 2,4-D removal was achieved, whereas isoproturon biodegradation was practically negligible. The presence of 2,4-D did not have a direct effect on acidogenesis since soluble organic carbon [expressed either as volatile fatty acids (VFAs) or as total organic carbon (TOC)] peaked within the first 10 days of operation in all bioreactors. Utilization of VFAs however appeared to follow two distinct patterns: one pattern was represented by acetate and butyrate (i.e. no acid accumulation) while the other was followed by propionate, isobuturate, valerate and isovalerate (i.e. acid accumulation, duration of which was related to the initial 2,4-D concentration). On the whole, all reactors exhibited a successful digestion performance demonstrated by complete VFAs utilization, considerable gas production (containing 45 to 65% methane by volume), substantial volatile suspended solids (VSS) reduction (42 to 50%), as well as pH and alkalinity recovery.     

渗滤液回灌频率对生物反应器填埋场的影响研究

通过模拟实验研究了渗滤液回灌周期为1、2、3和5 d的4个模拟垃圾柱的产甲烷过程和渗滤液水质的变化情况.在用NaOH调节回灌渗滤液pH值的前提下,回灌频率越高,模拟厌氧型生物反应器填埋垃圾柱先开始产甲烷,但当回灌周期低于3 d时,开始产甲烷的时间相差不多.从渗滤液水质看,回灌周期为3 d的垃圾柱渗滤液COD、VFA等有机污染物浓度下降最快.综合考虑启动时间、运行费用和填埋场的稳定进程,在厌氧型生物反应器填埋场中,实施3 d/次的渗滤液回灌频率最为合适.     

Enhancement of chemical-oxygen demand and color removal of distillery spent-wash by ozonation.

Distillery spent-wash has very high organic content (75,000 to 125,000 mg/L chemical-oxygen demand [COD]), color, and contains difficult-to-biodegrade organic compounds. For example, anaerobic treatment of the distillery spent-wash used in this study resulted in 60% COD reduction and low color removal. Subsequent aerobic treatment of the anaerobic effluent resulted in enhancement of COD removal to 66%. In this paper, the effect of ozonation on various properties of the anaerobically treated distillery effluent, including the effect on its subsequent aerobic biodegradation, was investigated. Ozonation of the anaerobically treated distillery effluent at various ozone doses resulted in the reduction of total-organic carbon (TOC), COD, COD/TOC ratio, absorbance, color, and increase in the biochemical-oxygen demand (BOD)/COD ratio of the effluent. Further, ozonation of the anaerobically treated distillery effluent at an ozone dose of 2.08 mg/mg initial TOC and subsequent aerobic biodegradation resulted in 87.4% COD removal, as compared to 66% removal when ozonation was not used.     

VFAs、TOC及COD作为生物除磷能力指标的探讨

在实际生活污水的处理中,研究了通过A/O运行模式对生物除磷过程中磷的变化情况及在厌氧释磷过程中COD、TOC与VFAs变化之间的关系。结果表明,在厌氧释磷过程中VFAs的变化更能准确地反映系统内释磷进程,实际生活污水中能直接用于磷释放的有机物含量占COD的13.33%,并且释放1 mg P所需VFAs为1.401 mg,此值明显低于前期研究结果。通过对COD、TOC和VFAs 3种组分的分析,可将实际生活污水中的有机底物分为3类:易生物降解含碳有机物、难降解的含碳有机物和水中存在的无机性还原物质,含量分别占COD的13.33%、31.7%和54.97%,其中只有13.33%的含量对生物释磷有直接作用,并可对实际生活污水除磷有指导意义。     

渗滤液耦合矿化垃圾制备甲烷氧化菌菌液

利用甲烷氧化菌菌液增加材料中甲烷氧化菌的数量,可以得到高甲烷氧化率的填埋场甲烷生物氧化覆盖材料。研究发现,渗滤液原水和渗滤液处理尾水均能促进甲烷氧化菌的生长,可利用渗滤液耦合矿化垃圾混合培养制备甲烷氧化菌菌液用于填埋场甲烷减排。填埋龄长的渗滤液原水有着较好的培养效果,得到的菌液在4 d内最高甲烷氧化速率达到2.68 mL/h,超过甲烷氧化菌培养液(nitrate minimal salt medium,NMS)的实验结果。渗滤液中总氮、无机碳、总有机碳和Ni元素的含量对甲烷氧化菌的培养过程影响较大,适用于甲烷氧化培养的渗滤液应满足:总氮1 400 mg/L,总有机碳55 mg/L,Ni元素0.4 mg/L,总磷含量较高。     

Recharge processes drive sulfate reduction in an alluvial aquifer contaminated with landfill leachate

Natural attenuation of contaminants in groundwater depends on an adequate supply of electron acceptors to stimulate biodegradation. In an alluvial aquifer contaminated with leachate from an unlined municipal landfill, the mechanism of recharge infiltration was investigated as a source of electron acceptors. Water samples were collected monthly at closely spaced intervals in the top 2 m of the saturated zone from a leachate-contaminated well and an uncontaminated well, and analyzed for delta(18)O, delta(2)H, non-volatile dissolved organic carbon (NVDOC), SO(4)(2-), NO(3)(-) and Cl(-). Monthly recharge amounts were quantified using the offset of the delta(18)O or delta(2)H from the local meteoric water line as a parameter to distinguish water types, as evaporation and methanogenesis caused isotopic enrichment in waters from different sources. Presence of dissolved SO(4)(2-) in the top 1 to 2 m of the saturated zone was associated with recharge; SO(4)(2-) averaged 2.2 mM, with maximum concentrations of 15 mM. Nitrate was observed near the water table at the contaminated site at concentrations up to 4.6 mM. Temporal monitoring of delta(2)H and SO(4)(2-) showed that vertical transport of recharge carried SO(4)(2-) to depths up to 1.75 m below the water table, supplying an additional electron acceptor to the predominantly methanogenic leachate plume. Measurements of delta(34)S in SO(4)(2-) indicated both SO(4)(2-) reduction and sulfide oxidation were occurring in the aquifer. Depth-integrated net SO(4)(2-) reduction rates, calculated using the natural Cl(-) gradient as a conservative tracer, ranged from 7.5x10(-3) to 0.61 mM.d(-1) (over various depth intervals from 0.45 to 1.75 m). Sulfate reduction occurred at both the contaminated and uncontaminated sites; however, median SO(4)(2-) reduction rates were higher at the contaminated site. Although estimated SO(4)(2-) reduction rates are relatively high, significant decreases in NVDOC were not observed at the contaminated site. Organic compounds more labile than the leachate NVDOC may be present in the root zone, and SO(4)(2-) reduction may be coupled to methane oxidation. The results show that sulfur (and possibly nitrogen) redox processes within the top 2 m of the aquifer are directly related to recharge timing and seasonal water level changes in the aquifer. The results suggest that SO(4)(2-) reduction associated with the infiltration of recharge may be a significant factor affecting natural attenuation of contaminants in alluvial aquifers.     

混合水解对打捆麦秸水解产酸的影响

为研究混合水解对麦秸水解产酸的影响，以猪粪、厨余和蔬菜废物为原料，研究其分别与麦秸混合水解产酸的特性，分析了水解过程中pH值、COD、SCOD和VFAs的变化。结果表明，除麦秸＋蔬菜废物最佳出料时间为3～9d外，麦秸、麦秸＋厨余垃圾、麦秸＋猪粪水解液最佳出料时间均为3～7d，7d后水解液COD浓度下降；将蔬菜废物与麦秸混合水解，水解液pH值降低幅度最大，水解液中总有机酸浓度最高，pH值最低为5．31，有机酸浓度最高达6．46g／L，且水解液中SCOD浓度、SCOD／COD比值最大；添加猪粪明显促进了麦秸有机物的水解溶出，麦秸单位干物质水解率和产酸率较对照分别提高了43％～134％和50．53％，但对提高水解液SCOD浓度、SCOD／COD比、TVFA浓度、降低水解液pH值的效果不如蔬菜废物；添加厨余垃圾的效果介于猪粪和蔬菜废物之间。从促进麦秸水解产酸的角度，以添加猪粪的效果最好。     

Degradation of herbicides in two sandy aquifers under different redox conditions.

We examined the potential for complete degradation (mineralisation) of the four [ring-U-14C]herbicides mecoprop, isoproturon, atrazine, and metsulphuron-methyl in two sandy aquifers representing aerobic, denitrifying, sulphate-reducing, and methanogenic conditions. Slurries with sediment and groundwater were set-up aerobically or anaerobically in the presence of the electron-acceptor prevailing at the sampling site, amended with 25 microg l(-1) herbicide, and incubated at 10 degrees C. Considerable mineralisation was only observed in sediment from the plough layer incubated aerobically. Here, 30% of 14C-mecoprop was recovered as 14CO2 after 15 days and 15% of isoproturon was recovered as 14CO2 after 267 days. Only 7% of mecoprop was recovered as 14CO2 after 313 days in sediment from the aquifer below sampled at 1.95-3.00 mbs (m below the surface). In denitrifying and methanogenic slurries, 3% of 14C added as mecoprop was recovered as 14CO2. Isoproturon was not mineralised except in the aerobic plough layer, and atrazine and metsulphuron-methyl were not mineralised under any of the conditions applied.     

运用GC-MS联用技术对垃圾渗滤液中有机污染物成分的分析

通过测定垃圾填埋场渗滤液的色度、BOD5、CODCr、TOC、NH3-N、NO-2-N、NO-3-N、TKN、TP、总硬度等指标来分析渗滤液的水质特性.利用GC-MS联用技术对渗滤液中有机污染物的组分进行了鉴定,共检测出主要有机污染物63种.     

Landfill leachate effects on sorption of organic micropollutants onto aquifer materials

The effect of dissolved organic carbon as present in landfill leachate, on the sorption of organic micropollutants in aquifer materials was studied by laboratory batch and column experiments involving 15 non-polar organic chemicals, 5 landfill leachates and 4 aquifer materials of low organic carbon content. The experiments showed that hydrophobic organic micropollutants do partition into dissolved organic carbon found in landfill leachate potentially increasing their mobility. However, landfill leachate interacted with aquifer materials apparently increases the sorbent affinity for the hydrophobic micropollutants. The combination of these two mechanisms affected the observed distribution coefficients within a factor of two, in some cases increasing and in other cases decreasing the sorption of the chemicals. No means for prediction of the effect is currently available, but from a practical point of view, the effect of landfill leachate on retardation of organic micropollutants in aquifer material seems limited.