Relating Cd2 + binding by humic acids to molecular weight: A modeling and spectroscopic study

Molecular weight(Mw) is a fundamental property of humic acids(HAs), which considerably affect the mobility and speciation of heavy metals in the environment. In this study, soil humic acid(HA) extracted from Jinyun Mountain, Chongqing was ultra-filtered into four fractions according to the molecular weight, and their properties were characterized.Complexation of cadmium was investigated by titration experiments. For the first time,Langmuir and non-ideal competitive adsorption-Donna(NICA-Donnan) models combined with fluorescence excitation-emission matrix(EEM) quenching were employed to elucidate the binding characteristics of individual Mw fractions of HA. The results showed that the concentration of acidic functional groups decreased with increasing Mw, especially the phenolic groups. The humification degree and aliphaticity increased with increasing Mw as indicated by elemental composition analysis and FT-IR spectra. The binding capacity of Cd~(2+) to Mw fractions of HA followed the order UF1( 5 kDa) UF2(5–10 kDa) UF4( 30 kDa) UF3(10–30 kDa). Moreover, the distribution of cadmium speciation indicated that the phenolic groups were responsible for the variations in binding of Cd~(2+) among different Mw fractions. The results of fluorescence quenching illustrated that the binding capacity of Cd~(2+) to Mw fractions was controlled by the content of functional groups, while the binding affinity was largely influenced by structural factors. The results provide a better understanding of the roles that different HA Mw fractions play in heavy metal binding,which has important implications in the control of heavy metal migration and bio-toxicity.     

Comparison between controlled landfill reactor and conditioned landfill bioreactor

Bioreactor landfills allow a more active landfill management that recognizes the biological, chemical and physical processes involved in a landfill environment. The laboratory-scale simulators of landfill reactors treating municipal solid wastes were studied, the effect of solid waste size, leachate recirculation, nutrient balance, pH value, moisture content and temperature on the rate of municipal solid waste (MSW) biodegradation were determined, and it indicated the optimum pH value, moisture content and temperature decomposing MSW. The results of waste biodegradation were compared with that of the leachate-recirculated landfill simulator and conservative sanitary landfill simulator. In the control experiment the antitheses of a decreasing trend of the organic load, measured as biological oxygen demand and chemical oxygen demand, was shown. An obvious enhancement of effective disposal from conservative sanitary landfill (CSL) simulator, to the leachate-recirculated landfill (LRL) simulator and to the conditioned bioreactor landfill(CBL) simulator would be noted, through displaying the compared results of solid waste settlement, heavy, metal concentration in leachate, methane production rate, biogas composition, BOD and COD as well as their ratio.     

Removal of refractory organics and heavy metals in landfill leachate concentrate by peroxi-coagulation process

Landfill leachate is a complex effluent and it is difficult to deal with. Electrochemical methods have been considered as a promising alternative technology for treatment of landfill leachate with refractory organic contaminants and heavy metals. Peroxi-coagulation (PC) process with iron anode and modified graphite felt cathode was developed for efficient landfill leachate concentrate treatment. Compared to electro-Fenton (EF) and electrocoagulation (EC) processes, the PC process was more cost-effective due to the combined action of ^•OH oxidation and iron hydroxides coagulation. A maximal TOC removal of 77.2% ± 1.4% was obtained after 360 min at initial pH = 5.0 and current density of 10 mA/cm². After the PC process, concentrations of all seven heavy metals in the final effluents were below the allowable emission limits given by the present regulatory standards. The method preference for heavy metal removal was PC > EC > EF. Based on the three-dimensional fluorescence spectroscopy coupled with regional integration analysis during the PC treatment, the florescence peaks of both humic acids and fulvic acids disappeared after treatment for 360 min. Decreasing trends were observed in the fluorescent regional standard volumes for aromatic protein I (31.4%), aromatic protein II (63.7%), fulvic acid-like (69.5%), soluble microbial by-product-like (75%) and humic acid-like regions (76.3%). The results indicate that comparing to the EF and EC process, the PC process provide a promising and more cost-effective alternative for the treatment of landfill leachate concentrate.     

Minimizing N_20 fluxes from full-scale municipal solid waste landfill with properly selected cover soil

Municipal solid waste landfills emit nitrous oxide(N_2O)gas.Assuming that the soil cover is the primary N_2O source from landfills, this study tested,during a four-year project,the hypothesis that the proper use of chosen soils with fine texture minimizes N_2O emissions.A full-scale sanitary landfill,a full-scale bioreactor landfill and a cell planted with Nerium indicum or Festuca arundinacea Schreb,at the Hangzhou Tianziling landfill in Hangzhou City were the test sites.The N_2O emission rates from all test sites were considerably lower than those reported in the published reports.Specifically,the N_2O emission rate was dependent on soil water content and nitrate concentrations in the cover soil.The effects of leachate recirculation and irrigation were minimal.Properly chosen cover soils applied to the landfills reduced N_2O flux.     

A simulation analysis of the migration and transformation of pollutants contained in landfill leachate

A dynamic composite model for a soil-water system that can be used to simulate the movement of leachate from a landfill. The composite model includes nine sub-models that trace water movement and the migration and transformation of five pollutants(organic N, NE4^- ,NO3^- , NO2^-, and Cl^ - ) in saturated and unsaturated soil. The model to simulate the movement of leachate from a landfill in Laogang Town,Shanghai City was used. In this application, the values for the model parameters were oblained by performing a laboratory simulation experimentof water movement and pollutant migration and transformation in soil columns. Soil and leachate obtained from the landfill site and its vicinitywere used in the laboratory experiments. The model was then used to simulate leachate movement and pollutant activity during the ten-year period when the landfill was in operation and in the twenty-year period following its closure. The simulation results revealed that the leachate migrated into the groundwater at the rate of 90-100 meters per year. This model can be applied in the design of future landfills in China for the purpose of assessing and forecasting leachate plumes.     

Minimizing N2O fluxes from full-scale municipal solid waste landfill with properly selected cover soil

Municipal solid waste landfills emit nitrous oxide （N2O） gas. Assuming that the soil cover is the primary N2O source from landfills, this study tested, during a four-year project, the hypothesis that the proper use of chosen soils with fine texture minimizes N2O emissions. A full-scale sanitary landfill, a full-scale bioreactor landfill and a cell planted with Nerium indicum or Festuca arundinacea Schreb, at the Hangzhou Tianziling landfill in Hangzhou City were the test sites. The N2O emission rates from all test sites were considerably lower than those reported in the published reports. Specifically, the N2O emission rate was dependent on soil water content and nitrate concentrations in the cover soil. The effects of leachate recirculation and irrigation were minimal. Properly chosen cover soils applied to the landfills reduced N2O flux.     

Achieving nitritation at low temperatures using free ammonia inhibition on Nitrobacter and real-time control in an SBR treating landfill leachate

Free ammonia(FA) inhibition on nitrite-oxidized bacteria(NOB) and real-time control are used to achieve nitrogen removal from landfill leachate via nitrite pathway at low temperatures in sequencing batch reactor. The inhibition of FA on NOB activity during the aerobic period was prolonged using real-time control. The degree of nitrite accumulation was monitored along with variations of the ammonia-oxidizing bacteria and NOB population using fluorescence in situ hybridization techniques. It is demonstrated that the end-point of ammonia oxidization is detected from the on-line measured dissolved oxygen,oxidization–reduction potential, and p H signals, which could avoid the loss the FA inhibition on NOB caused by excess aeration. At low temperature(13.0–17.6°C), the level of nitrite pathway rapidly increased from 19.8% to 90%, suggesting that nitritation was successfully started up at low temperature by applying syntrophic association of the FA inhibition and real-time control, and then this high level of nitrite pathway was stably maintained for as long as 233 days. Mechanism analysis shows that the establishment of nitritation was primarily the result of predominant ammonia-oxidizing bacteria developed in the nitrifying bacteria population compared to NOB. This was mainly due to a gradual reduction of nitrite amount that is available to provide energy for the growth of NOB,eventually leading to the elimination of NOB from the bacterial clusters in sequencing batch reactor sludge system.     

Control factors of partial nitritation for landfill leachate treatment

Anaerobic ammonium oxidation (ANAMMOX) technology has potential technical superiority and economical efficiency for the nitrogen removal from landfill leachate, which contains high-strength ammonium nitrogen (NH4 -N) and refractory organics. To complete the ANAMMOX process, a preceding partial nitritation step to produce the appropriate ratio of nitrite/ammonium is a key stage. The objective of this study was to determine the optimal conditions to acquire constant partial nitritation for landfill leachate treatment, and a bench scale fixed bed bio-film reactor was used in this study to investigate the effects of the running factors on the partial nitritation. The results showed that both the dissolved oxygen (DO) concentration and the ammonium volumetric loading rate (Nv) had effects on the partial nitritation. In the controlling conditions with a temperature of 30±1℃, Nv of 0.2-1.0 kg NH4 -N/(m3d), and DO concentration of 0.8-2.3 mg/L, the steady partial nitritation was achieved as follows: more than 94% partial nitritation efficiency (nitrite as the main product), 60%-74% NH4 -N removal efficiency, and NO2--N/NH4 -N ratio (concentration ratio) of 1.0-1.4 in the effluent. The impact of temperature was related to iVv at certain DO concentration, and the temperature range of 25-30癈 was suitable for treating high strength ammonium leachate. Ammonium-oxidizing bacteria could be acclimated to higher FA (free ammonium) in the range of 122-224 mg/L. According to the denaturing gradient gel electrophoresis analysis result of the bio-film in the reactor, there were 25 kinds of 16S rRNA gene fragments, which indicated that abundant microbial communities existed in the bio-film, although high concentrations of ammonium and FA may inhibit the growth of the nitrite-oxidizing bacteria and other microorganisms in the reactor.     

Trihalomethane formation potential of organic fractions in secondary effluent

Organic matter is known to be the precursor of numerous chlorination by-products. Organic matter in the secondary e uent from the Wenchang Wastewater Treatment Plant (Harbin, China) was physically separated into the following fractions: particulate organic carbon (1.2–0.45 m), colloidal organic carbon (0.45–0.1 m), fine colloidal organic carbon (0.1–0.025 m), and dissolved organic carbon (DOC) (< 0.025 m). Moreover, < 0.45 m fraction was chemically separated into hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N), and hydrophilic fraction (HPI). The chlorine reactivity of these organic fractions obtained from both size and XAD fractionations were evaluated. The structural and chemical compositions of the HPO-A, HPO-N, TPI-A, and TPI-N isolates were characterized using elemental analysis (C, H, O, and N), Fourier transform infrared spectroscopy (FT-IR), and proton nuclear magnetic resonance spectroscopy (1H-NMR). Results showed that DOC was dominant in terms of total concentration and trihalomethane formation potential (THMFP), and there was no statistical di erence in both specific THMFP (STHMFP) and specific ultraviolet light absorbance among the 0.45, 0.1, and 0.025 m filtrates. HPO-A had the highest STHMFP compared to other chemical fractions. HPO-A, HPO-N, TPI-A, and TPI-N contained 3.02%–3.52% of nitrogen. The molar ratio of H/C increased in the order of HPO-A < HPO-N < TPI-A < TPI-N. The O/C ratio was relatively high for TPI-N as compared to those for the other fractions. 1H-NMR analysis of the four fractions indicated that the relative content of aromatic protons in HPO-A was significantly higher than those in the others. The ratio of aliphatic to aromatic protons increased in the order of HPO-A < HPO-N < TPI-A < TPI-N. FT-IR analysis of the four fractions showed that HPO-A had greater aromatic C==C content whereas HPO-N, TPI-A, and TPI-N had greater aliphatic C–H content. TPI-N contained more oxygen-containing functional groups than the other fractions.     

Evolution on qualities of leachate and landfill gas in the semi-aerobic landfill

To study the characteristics of stabilization in semi-aerobic landfill, large-scale simulated landfill was constructed based on the semiaerobic landfill theory. Consequently, the concentrations of chemical oxygen demand (COD), ammonia nitrogen, and nitrite nitrogen, and the pH value in leachate, as well as the component contents of landfill gas composition (methane, carbon dioxide, and oxygen) in landfill were regularly monitored for 52 weeks. The results showed that COD and ammonia concentrations declined rapidly and did not show the accumulating rule like anaerobic landfill, and remained at about 300 and 100 mg/L, respectively, after 48 weeks. Meanwhile, the descending rate reached 98.9% and 96.9%, respectively. Nitrate concentration increased rapidly after 24 weeks and fluctuated between 220–280 mg/L after 43 weeks. The pH values were below 7 during the first 8 weeks and after that leachates appeared to be alkaline. Carbon dioxide was the main composition in landfill gas and its concentration remained at a high level through the whole stabilization process. The average contents of carbon dioxide, oxygen, and methane varied between 19 vol.%–28 vol.%, 2 vol.%–8 vol.%, and 5 vol.%–13 vol.%, respectively. A relative equilibrium was reached after 48 weeks. The highest temperature in the landfill chamber could amount to 75.8 degrees centigrade.     

稠油废水中溶解性有机物的分离和表征

利用XAD-8大孔吸附树脂将稠油废水中的溶解性有机物进行分离,对稠油废水DOM及各分离组分进行TOC、UV254、硬度、Ca2+、Mg2+浓度等的测定,并采用官能团滴定、红外光谱等分析方法对稠油废水进行表征。结果表明:稠油废水中DOM以包括腐殖酸和富里酸两部分物质的憎水部分为主,两者分别占总TOC的18.64%和43.58%,亲水部分仅占9.35%,同时还有一部分有机物未分离出;紫外吸光度结果表明,稠油废水及各组分的芳香化程度为:腐殖酸>富里酸>稠油废水>亲水部分;官能团滴定结果表明,各组分的总酸度大小为富里酸>腐殖酸>亲水部分;稠油废水中DOM及各组分的硬度和Ca2+、Mg2+分布分析结果表明,腐殖酸和富里酸均和Ca2+、Mg2+发生反应,由此可推断由于腐殖酸和富里酸与交换下来的Ca2+、Mg2+的吸附作用导致两者可能因此粘附在大孔弱酸树脂上,从而影响树脂正常运行;红外光谱分析结果与官能团滴定结果一致。     

高DOM渗滤液厌氧-好氧-混凝处理工艺

采用厌氧-好氧-混凝工艺,对垃圾焚烧厂高DOM渗滤液进行处理,当进水ρ(COD_Cr)平均值为10 800 mg/L时,出水ρ(COD_Cr)平均值可达208 mg/L;同时,着重针对各工艺单元出水DOM不同分子质量分布区间的ρ(COD_Cr)以及DOM组成成分的变化进行了研究.结果表明:该处理工艺对DOM分子质量＜50 ku的有机物去除率均可达到94.7%以上,而对分子质量＜2 ku的有机物的去除率可达99.0%;对渗滤液DOM组成成分〔腐殖酸(HA)、富里酸(FA)和亲水性有机质(HyI)〕的去除率均达到90.0%以上,表明该组合工艺用于处理垃圾焚烧厂渗滤液是可行的.      

三峡库区填埋场和焚烧厂渗滤液水质季节性差异

分析了重庆长生桥垃圾填埋场和同兴焚烧厂渗滤液在常规水质和溶解性有机质组成结构方面的季节性差异. 结果表明,填埋场渗滤液在夏季的ρ(COD_Cr), ρ(TOC), ρ(BOD₅),ρ(BOD₅)/ρ(COD_Cr)和ρ(VFA)均高于其他季节,相应指标在冬季最低,但ρ(NH₃-N)和 pH的季节性差异不明显. 填埋场渗滤液中DOM组成结构的季节性差异较大,表现在冬季渗滤液中HA所占比例最高,为16.1%,而春、夏季分别为6.6%和8.1%;冬季渗滤液中HyI所占比例最低,为32.7%,其他季节为41.9%～43.5%;ρ(FA)的季节性差异相对较小. 填埋场中ρ(FA)/ρ(HA)的季节性差异较大,夏季较高,冬季较小. 焚烧厂渗滤液的常规水质,DOM的构成及ρ(FA)/ρ(HA)的季节性差异均很小.      

垃圾焚烧厂渗滤液处置工艺中溶解性有机物变化特性

采用“物化+生物处理+深度处理”组合工艺处理垃圾焚烧厂渗滤液,探索组合工艺对渗滤液的实际去除效果,考察渗滤液中溶解性有机物(DOM)的组成及其结构特性随组合工艺的变化规律,并对其机理进行了初步探讨.结果表明,当进水COD和氨氮的平均值分别为17825,1946mg/L时,组合工艺对渗滤液中COD和氨氮去除率均达到99%左右,出水COD、氨氮、色度分别为57mg/L、5mg/L、15倍.组合工艺对渗滤液DOM中腐殖酸(HA)、富里酸(FA)和亲水性有机物(HyI)的去除率均达到99%左右,对HA、FA、HyI削减显著的工艺单元分别为混凝2、厌氧和颗粒活性炭(GAC),削减率分别达到86%、77%和84%.出水HA、FA和HyI的COD浓度分别为10,23,6mg/L,其中分子量较小的FA为出水主要组分.随着组合工艺处理过程的进行,渗滤液中DOM的紫外区吸光度值显著下降,DOM的E254、E253/E203分别由1.55、0.64下降至0.012和0.024,说明DOM的芳香性和复杂程度显著降低,脂肪链芳香化合物逐渐增加;此外,E300/E400和E465/E665分别由2.65和2.17增加至9.78和8.03,表明渗滤液中溶解性有机物腐殖化程度不断降低,芳香构化程度不断减小.     

松花江水中天然有机物的提取分离与特性表征

将反渗透与XAD大孔树脂吸附技术相结合,对松花江水中天然有机物(NOM)进行了浓缩和分离,并采用紫外光谱、红外光谱、液相凝胶色谱、官能团滴定1、HNMR核磁共振等分析手段,对松花江水中NOM及其各分离组分和一种商用腐殖酸CHA的特性进行了比较和表征.结果表明,利用反渗透进行NOM浓缩对水中有机物具有很高的回收率;松花江水中NOM组成为:富里酸>腐殖酸>亲水部分;各组分芳香性为:腐殖酸>憎水部分>富里酸>亲水部分,E₄/E₆与芳香性之间缺乏必然的联系;腐殖酸和商用腐殖酸具有较高的不饱和性,NOM和亲水部分次之,憎水部分和富里酸中饱和烃含量较多;紫外吸收较弱的有机成分对NOM分子量的贡献较大;NOM及其分离组分的总酸度为9.84～12.15meq/g,羧酸含量为CHA>亲水>憎水>NOM>富里酸>腐殖酸;NOM及其各分离组分的溶解性有机物构成以脂肪烃为主.     

填埋场渗滤液腐殖酸随填埋龄的变化特性及模型研究

以福建省12个不同填埋场渗滤液作为研究对象,分析了不同填埋龄渗滤液中腐殖酸的性质随填埋龄的变化关系.结果表明,渗滤液中富里酸(FA)浓度和比例都高于胡敏酸(HA),且HA、FA和腐殖酸(HS)的浓度都随着填埋龄的增加呈先上升后下降,HA所占比例随填埋龄的增加呈先上升后下降的趋势,而FA和HS则是先上升,后呈波动变化.HA、FA的E280、E300/E400和E465/E665的分析结果表明HA较FA有更多的芳环结构,更大的分子量和较高腐殖化程度;随着填埋龄的增加,HA的腐殖化程度呈下降趋势,而FA则呈上升趋势;HA和FA的E300/E400和E465/E665随填埋龄的增加并未有明显的变化趋势.根据有机物降解动力学原理建立模型,分别对HA、FA和HS的浓度和填埋龄的变化关系进行拟合,结果表明模型的模拟值和实测值具有较好的一致性,HA、FA和HS模拟值和实测值的相关系数R2分别为0.820、0.932和0.946.表明该模型能有效模拟和预测腐殖酸随填埋龄的浓度变化关系.     

腐蚀电池-Fenton处理渗滤液溶解性有机物光谱特征

为了研究垃圾渗滤液中溶解性有机物（DOM）在腐蚀电池-Fenton（CCF）深度处理过程中的去除特性,采用XAD-8和XAD-4树脂将DOM分成5种组分（亲水性有机物HPI、疏水性有机酸HPO-A、过渡亲水性有机酸TPI-A、疏水性中性有机物HPO-N、过渡亲水性中性有机物TPI-N）,并用紫外和荧光光谱对各组分的降解...     

渗滤液场内处理的有机物去除特征和植物毒性评价

摘要：以3种不同处理水平的渗滤液为研究对象,从有机物去除特征和植物毒性角度研究通过渗滤液循环回灌和终场覆盖层灌溉2个单元处理生活垃圾填埋场渗滤液的可行性.结果表明,循环回灌对老港渗滤液中的小分子量亲水性物质类(HyI)有机物去除效果较好,去除率为91.2%;终场覆盖层灌溉对循环回灌出水中的高分子量腐殖质类(HS)有机物去除效果较佳,去除率为85.7%;两者串联组合的场内循环处理工艺对老港渗滤液中的溶解性有机物(DOM)去除 率高达96.9%,且对HS和HyI均具较高的去除效果,去除率分别为96.6%和97.0%;循环回灌和覆盖层灌溉这2个处理单元还具有梯级降低渗滤液植物毒性的作用.     

生活垃圾填埋场垃圾腐殖质组成和变化规律的表征

通过分析上海老港生活垃圾填埋场填埋垃圾的腐殖质组成和光密度,考察了填埋垃圾的腐殖质组成和光学特性随填埋龄的变化规律.研究结果表明,填埋龄在1～14 a间的填埋垃圾中腐殖质组分的有机碳绝对含量的波动幅度很大,而腐殖质组分相对含量具有比较明显的变化规律,其中腐殖质总可提取率和wHA/wFA比值分别随填埋龄增加呈线性下降和上升的趋势.另一方面,填埋垃圾腐殖质光学特性研究表明,填埋垃圾可提取腐殖质和富里酸组分的E4/E6比值随填埋龄变化无明显关系,而胡敏酸的E4/E6比值则随填埋龄的增加呈线性下降趋势.因此,填埋垃圾腐殖质的总可提取率、wHA/wFA比值以及胡敏酸组分的E4/E6比值可有效地表征填埋垃圾和填埋场的稳定化进程.     

Fenton法处理垃圾渗滤液过程中有机物分子质量分布和荧光特性

采用Fenton氧化工艺对上海某垃圾填埋场垃圾渗滤液进行处理. 提取和分离了Fenton氧化前后腐殖酸组分(富里酸、胡敏酸),运用凝胶色谱法和三维荧光光谱技术对Fenton氧化前后各物质的分子质量分布和有机物荧光特性进行了研究. 结果表明:Fenton反应可使ρ(BOD₅)/ρ(COD_Cr)从0.011提高到0.285. 通过分子质量分布和三维荧光特性的测量可知,造成这种可生化性提高的原因是Fenton反应使垃圾渗滤液中有机物的分子质量降低,其中对高分子质量胡敏酸的去除以及对富里酸分子质量的降低起到了关键作用.