Fluorescence of sediment humic substance and its effect on the sorption of selected endocrine disruptors

Humic substances (HS) have a critical influence on the sorption of organic contaminants by soils and sediments. This paper describes investigations into the sorption behavior of three representative endocrine disruptors, bisphenol A (BPA), 17beta-estradiol (E2), and 17alpha-ethynylestradiol (EE2), onto sediments and HS extracted sediments using a batch technique. The organic carbon-normalized partition coefficients (K(oc)) for the extracted HS (K(oc)(hs)) were calculated, and the fluorescence spectra of the HS extraced from different sediment samples were gained using excitation/emission matrix (EEM). Particular attention was paid to the correlations between the fluorescence characteristics of HS and the log K(oc)(hs) of selected endocrine disruptors. The results show that the log K(oc)(hs) values range from 3.14 to 4.09 for BPA, from 3.47 to 4.33 for E2, and from 3.65 to 4.32 for EE2. Two characteristic excitation-emission peaks were observed for HS samples extracted from sediments. They are located at Ex/Em=250-260 nm/400-450 nm (peak alpha') and Ex/Em=310-330 nm/390-400 nm (peak alpha) respectively. The alpha' and alpha peak relative intensities I(alpha')/I(alpha) vary from 0.46 to 1.64 for different extracted HS samples. The similarity between fulvic acids (FA) Ex/Em pairs and those observed for HS indicates that FA is the predominant fraction of HS extracted from sediments. Moreover, the log K(oc)(hs) values of BPA, E2, and EE2 have a negative linear correlation to I(alpha')/I(alpha) values. Peak alpha is often attributed to relatively stable and high molecular weight aromatic fulvic-like matter. Therefore, the result presented here reveals that the abundance of aromatic rings in HS molecular structure plays a critical role in the sorption of selected endocrine disruptors.     

Dissolved organic matter with multi-peak fluorophores in landfill leachate

Dissolved organic matter (DOM) sampled from municipal landfill leachate of different ages with/without anoxic or aerobic treatment, was intensively fractionated via size exclusion chromatography (SEC) and hydrophobic resins, and was studied with fluorescence excitation and emission matrix (EEM). Six fluorophores with multiple EEM peaks (fluorophore A-F) were identified based on the collected EEM spectra and validated by bi-variate analysis, principal component analysis, and parallel factor analysis, as follows (excitation wavelength Ex and emission wavelength Em): (Ex 240, 310, 360 nm, Em 460 nm), (Ex 220, 280 nm, Em 340 nm), (Ex 220, 270 nm, Em 300 nm), (Ex 220, 280 nm, Em 360 nm), (Ex 230, 320 nm, Em 420 nm) and (Ex 220, 310 nm, Em 400 nm). The spectral characteristics of these fluorophores were discussed using fractional EEM and apparent molecular weight (AMW) data obtained via SEC analysis. The triple peak flurophore A was pointed at a hydrophobic acid or hydrophobic neutral compound with a pyrenyl functional group of AMW 2500-3500 Da, which displayed an excitation wavelength at 360 nm and a fluorescence intensity ratio of 6.70(+/-1.79):1.70(+/-0.41):1 (fluorescent intensities of Ex 240:Ex 310:Ex 360 nm at Ex 460 nm). This compound is observed to be refractory in landfilling or in anoxic/aerobic treatments, and is specific to this leachate contamination. This paper revealed that the coupling of SEC and EEM can be useful to track the fluorescent DOM fraction in landfill leachate.     

Characterizing the interactions between polycyclic aromatic hydrocarbons and fulvic acids in water

Polycyclic aromatic hydrocarbons (PAHs) are persistent, bioaccumulative, and toxic chemicals and are listed as priority pollutants by the US EPA. Although they are sparsely soluble in water, their solubility can be increased by binding to dissolved organic matter in natural waters, which will further increase their environmental risk as toxic pollutants. In this study, the interaction between PAHs, exemplified by fluorene and anthracene, and fulvic acid (FA) was studied using fluorescence quenching titration method with fluorescence emission spectra, respectively. The association of FA with the mixture of fluorene and anthracene was also evaluated by excitation–emission matrix (EEM) fluorescence spectrometry combined with parallel factor (PARAFAC) analysis. Results demonstrate that EEM fluorescence spectrometry with PARAFAC analysis was sensitive and reliable to determine the binding properties of PAHs with FA in a mixed aqueous solution. The conditional stability constants and binding capacities show that both PAHs bind to FA tightly.     

Investigating the effect of landfill leachates on the characteristics of dissolved organic matter in groundwater using excitation–emission matrix fluorescence spectra coupled with fluorescence regional integration and self-organizing map

For the purpose of investigating the effect of landfill leachate on the characteristics of organic matter in groundwater, groundwater samples were collected near and in a landfill site, and dissolved organic matter (DOM) was extracted from the groundwater samples and characterized by excitation–emission matrix (EEM) fluorescence spectra combined with fluorescence regional integration (FRI) and self-organizing map (SOM). The results showed that the groundwater DOM comprised humic-, fulvic-, and protein-like substances. The concentration of humic-like matter showed no obvious variation for all groundwater except the sample collected in the landfill site. Fulvic-like substance content decreased when the groundwater was polluted by landfill leachates. There were two kinds of protein-like matter in the groundwater. One kind was bound to humic-like substances, and its content did not change along with groundwater pollution. However, the other kind was present as “free” molecules or else bound in proteins, and its concentration increased significantly when the groundwater was polluted by landfill leachates. The FRI and SOM methods both can characterize the composition and evolution of DOM in the groundwater. However, the SOM analysis can identify whether protein-like moieties was bound to humic-like matter.     

Interaction of erythromycin ethylsuccinate and acetaminophen with protein fraction of extracellular polymeric substances (EPS) from various bacterial aggregates

Extracellular polymeric substances (EPS) are, along with microbial cells, the main components of the biological sludges used in wastewater treatment and natural biofilms. EPS play a major role in removing pollutants from water by means of sorption. The ability of soluble EPS (S-EPS) and bound EPS (B-EPS) derived from various bacterial aggregates (flocs, granules, biofilms) to bind at pH 7.0?±?0.1 to two pharmaceutical substances, acetaminophen (ACE) and erythromycin ethylsuccinate (ERY), has been investigated using the fluorescence quenching method. Two intense fluorescence peaks, A (Ex/Em range, 200–250/275–380 nm) and B (Ex/Em range, 260–320/275–360 nm), corresponding respectively to the aromatic protein region and soluble microbial by-product-like region, were identified in a three-dimensional excitation-emission matrix of EPS samples. The fluorescence peak, which corresponds to humic-like substances, was also identified though at low intensity. The ability of EPS to bind ACE was found to exceed that for ERY. The aromatic protein fraction of EPS displays a slightly higher affinity for drugs than that shown by the soluble microbial by-product-like fraction. The S-EPS and B-EPS present the same affinity for ACE and ERY. The effective quenching constants (log K) derived from the Stern–Volmer Equation equaled at peak A (with S-EPS): 3.7?±?0.2 to 4.0?±?0.1 for ACE and 2.1?±?0.3 to 2.7?±?0.1 for ERY. With B-EPS, these values were 3.9?±?0.1 to 4.0?±?0.1 for ACE and 2.0?±?0.2 to 2.6?±?0.1 for ERY. Our results suggest that the weaker EPS affinity for ERY than for ACE serves to partially explain why only about 50–80 % of ERY is removed from wastewater at the treatment plant. Moreover, this work demonstrates that EPS from natural river biofilms are able to bind drugs, which in turn may limit the mobility of drugs in natural waters.     

Ozonation effects on emerging micropollutants and effluent organic matter in wastewater: characterization using changes of three-dimensional HP-SEC and EEM fluorescence data

The degradation of effluent organic matter (EfOM) in a municipal wastewater treated by ozonation was characterized using the methods of high-performance size-exclusion chromatography (HP-SEC) and excitation/emission matrix (EEM) fluorescence combined with parallel factor analysis (PARAFAC). The removal of 40 diverse trace-level contaminants of emerging concern (CEC) present in the wastewater was determined as well. Ozonation caused a rapid decrease of the absorbance and fluorescence of the wastewater, which was associated primarily with the oxidation of high and low apparent molecular weight (AMW) EfOM fractions. PARAFAC analysis also showed that components C1 and C2 decreased prominently in these conditions. The EfOM fraction of intermediate molecular weight ascribable to a terrestrial humic-like component (C3) tended to be less reactive toward ozone. Relative changes of EEM fluorescence were quantified using F _max values of PARAFAC-identified components (∆F/F ⁰ _max). Unambiguous relationships between ∆F/F ⁰ _max values and the extent of the degradation of the examined CECs (∆C/C₀) were established. This allowed correlating main parameters of the ∆C/C₀ vs. ∆F/F ⁰ _max relationships with the rates of oxidation of these CECs. The results demonstrate the potential of online measurements of EEM fluorescence for quantitating effects of ozonation on EfOM and micropollutants in wastewater effluents.

     

Characterizing the heavy metal-complexing potential of fluorescent water-extractable organic matter from composted municipal solid wastes using fluorescence excitation–emission matrix spectra coupled with parallel factor analysis

To investigate the effect of organic matter evolution on heavy metal sorption, fluorescence excitation–emission matrix (EEM) spectra combined with parallel factor (PARAFAC) analysis were employed to characterize the evolution and metal-complexing potential of fluorescent water-extractable organic matter (WEOM) from composted municipal solid wastes (MSWs). The WEOMs examined comprised humic-, fulvic-, tryptophan-, and tyrosine-like substances. Composting treatment increased the content of humic- and fulvic-like matter, and changed the existence pattern of tryptophan- and tyrosine-like substances (i.e., the tryptophan- and tyrosine-like substances from uncomposted MSWs were mainly bound in protein-like matter, whereas those from composted MSWs were primarily bound in humic- and fulvic-like substances). Furthermore, composting treatment increased the polar functional group, aromaticity, and humification degree of the WEOMs, but decreased the aliphatic and hydroxyl group. These evolutions decreased the Cu(II) affinities of fulvic- and humic-like substances and the Pb(II) affinities and complexing capacities of fulvic-like substances, but increased the Cu(II) complexing capacities of fulvic- and humic-like substances. These results reveal that mature composts from the MSWs can be used for the remediation of Cu- and Pb-contaminated soils in situ, whereas immature composts can enhance the metal transferability from soil to plant.     

Multivariate curve resolution of multidimensional excitation-emission quenching matrices of a Laurentian soil fulvic acid

Fluorescence excitation–emission matrices (EEM) of aqueous solutions of Laurentian soil fulvic acid (LFA) at three concentrations (50, 75 and 100 mg/l) were obtained at two pH values (pH = 4.0 and 6.0) and as function of the Cu(II) ion concentration. The presence of Cu(II) ion provokes quenching of the intrinsic LFA fluorescence due to complex formation. Multivariate curve resolution (MCR-ALS) was used to successfully decompose single EEM into excitation and emission spectra for the detected components. Moreover, multidimensional (up to six dimensions) data matrices were generated by adding EEM collected as function of the LFA and Cu(II) concentrations and pH. MCR-ALS was able to resolve the excitation and emission spectra from these multidimensional data matrices given further information about the spectral variation profiles induced by the experimental factors. Conditional stability constants (log K_LFACu) were calculated from the quenching profiles observed as function of the Cu(II) concentration, as well as, their trends as function of pH and LFA concentration were obtained – average (and standard deviation) of log K_LFACu = 4.6 ± 0.2. This EEM/MCR-ALS methodology constitutes a new tool for the study of natural organic matter under varying experimental conditions that characterize natural environmental systems.     

Size and composition distributions of particulate matter emissions: part 2--heavy-duty diesel vehicles

Particulate matter (PM) emissions from heavy-duty diesel vehicles (HDDVs) were collected using a chassis dynamometer/dilution sampling system that employed filter-based samplers, cascade impactors, and scanning mobility particle size (SMPS) measurements. Four diesel vehicles with different engine and emission control technologies were tested using the California Air Resources Board Heavy Heavy-Duty Diesel Truck (HHDDT) 5 mode driving cycle. Vehicles were tested using a simulated inertial weight of either 56,000 or 66,000 lb. Exhaust particles were then analyzed for total carbon, elemental carbon (EC), organic matter (OM), and water-soluble ions. HDDV fine (< or =1.8 microm aerodynamic diameter; PM1.8) and ultrafine (0.056-0.1 microm aerodynamic diameter; PM0.1) PM emission rates ranged from 181-581 mg/km and 25-72 mg/km, respectively, with the highest emission rates in both size fractions associated with the oldest vehicle tested. Older diesel vehicles produced fine and ultrafine exhaust particles with higher EC/OM ratios than newer vehicles. Transient modes produced very high EC/OM ratios whereas idle and creep modes produced very low EC/OM ratios. Calcium was the most abundant water-soluble ion with smaller amounts of magnesium, sodium, ammonium ion, and sulfate also detected. Particle mass distributions emitted during the full 5-mode HDDV tests peaked between 100-180 nm and their shapes were not a function of vehicle age. In contrast, particle mass distributions emitted during the idle and creep driving modes from the newest diesel vehicle had a peak diameter of approximately 70 nm, whereas mass distributions emitted from older vehicles had a peak diameter larger than 100 nm for both the idle and creep modes. Increasing inertial loads reduced the OM emissions, causing the residual EC emissions to shift to smaller sizes. The same HDDV tested at 56,000 and 66,000 lb had higher PM0.1 EC emissions (+22%) and lower PM0.1 OM emissions (-38%) at the higher load condition.     

Fluorescence spectroscopic characterization of DOM fractions isolated from a filtered river water after ozonation and catalytic ozonation

Fluorescence spectra were applied to investigate the structural changes of four dominant dissolved natural organic matter (DOM) fractions of a filtered river water before and after ozonation and catalytic ozonation. The ozonation and catalytic ozonation with synthetic goethite (FeOOH) and cerium dioxide (CeO(2)) were carried out under normal conditions, i.e. pH 7, reaction time of 10 min, and ozone/DOC ratio of about 1. The fluorescence spectra were recorded at both excitation-emission matrix (EEM) and synchronous scanning modes. EEM results reveal that ozonation of these DOM fractions causes a significant decrease of the aromaticity of humic-like structures and an increase of electron withdrawing groups, e.g., carboxylic groups. The catalysts can further improve the destruction of the humic-like structures in catalytic ozonation. Synchronous spectra reveal that ozonation of hydrophobic acid and hydrophilic acid (HIA) yields a significant amount of by-products with low aromaticity and low molecular weight. Catalytic ozonation enhances substantially the formation of these by-products from HIA and improves the destruction of highly polycyclic aromatic structures for all examined DOM fractions.     

改良型AO法组合工艺中有机物的三维荧光分析

采用三维荧光(EEM)光谱技术,对上海竹园第二污水处理厂改良型AO法组合工艺运行过程中的各种溶解性有机物(DOM)进行分析,并对比研究传统好氧活性污泥法曝气池出水和A/O脱氮工艺硝化池出水DOM的EEM光谱的迁移变化特性.结果表明,各种DOM中主要的荧光物质有类蛋白质(荧光峰A和B)及类腐殖质(荧光峰C),经改良型AO法组合工艺处理后,荧光峰的强度降低了14％～60％,同时类蛋白质和腐殖质的结构也发生了变化;腐殖酸溯源表明DOM中的腐殖酸以微生物代谢产生的带有荧光基团的腐殖酸类为主.     

回灌型准好氧填埋场脱氮特性及加速稳定化研究

采用2个模拟填埋生物反应器,1号柱渗滤液简单回灌,2号柱为渗滤液回灌准好氧联合运行方式,研究了渗滤液回灌准好氧生物反应器填埋场的脱氮特性及加速垃圾稳定化特性.研究结果表明:渗滤液回灌准好氧填埋场具有很强的脱氮能力,2号柱由厌氧运行方式改为准好氧条件下,渗滤液中的氨氮和凯式氮浓度分别由最大值的3 198 mg/L和3 345 mg/L降低到第160 d的73 mg/L和81 mg/L,去除率分别为97.7%和97.6%,pH快速升高到8.0左右,COD浓度快速降低.渗滤液中溶解性有机物(DOM)分级结果表明,2号柱HA和FA含量的增加明显快于1号柱.2号柱DOM的三维荧光光谱特性发生了较大变化,荧光基团从60 d结构简单的类蛋白物质转变为95 d结构复杂的类胡敏酸和富里酸物质,而l号柱渗滤液DOM荧光基团一直是结构简单的类蛋白物质.结果表明回灌准好氧生物反应器填埋场的稳定化速度远快于简单回灌的生物反应器填埋场.     

Spectroscopic characterization of water extractable organic matter during composting of municipal solid waste

This paper aims to characterize the evolution of water extractable organic matter (WEOM) during the composting of municipal solid waste (MSW), and investigate the correlation between maturity and WEOM characteristics. WEOM was extracted at different stages of MSW composting (0, 7, 14, 21, and 51 d) and characterized by FTIR, UV-Vis, and fluorescence spectroscopy. The results obtained show that the composting process decreased aliphatics, alcohols, polysaccharides, as well as protein-like materials, and increased aromatic polycondensation, humification, oxygen-containing functional groups, molecular weight, and humic-like materials. The maturity of MSW during composting was characterized by the presence of the peak with an excitation/emission wavelength pair of 289/421 nm in excitation-emission matrix spectra.     

Colloidal diatomite, radionickel, and humic substance interaction: a combined batch, XPS, and EXAFS investigation

This work determined the influence of humic acid (HA) and fulvic acid (FA) on the interaction mechanism and microstructure of Ni(II) onto diatomite by using batch experiments, X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS) methods. Macroscopic and spectroscopic experiments have been combined to see the evolution of the interaction mechanism and microstructure of Ni(II) in the presence of HA/FA as compared with that in the absence of HA/FA. The results indicated that the interaction of Ni(II) with diatomite presents the expected solution pH edge at 7.0, which is modified by addition of HA/FA. In the presence of HA/FA, the interaction of Ni(II) with diatomite increased below solution pH 7.0, while Ni(II) interaction decreased above solution pH 7.0. XPS analysis suggested that the enrichment of Ni(II) onto diatomite may be due to the formation of (≡SO)₂Ni. EXAFS results showed that binary surface complexes and ternary surface complexes of Ni(II) can be simultaneously formed in the presence of HA/FA, whereas only binary surface complexes of Ni(II) are formed in the absence of HA/FA, which contribute to the enhanced Ni(II) uptake at low pH values. The results observed in this work are important for the evaluation of Ni(II) and related radionuclide physicochemical behavior in the natural soil and water environment.     

Influence of n-alkanes and petroleum on fatty acid composition of a hydrocarbonoclastic bacterium: Marinobacter hydrocarbonoclasticus strain 617

This study concerns the effects of various long-chain n-alkanes, n-alkane mixtures and Arabian Light crude oil on the fatty acid (FA) composition of a sedimentary marine bacteria (Marinobacter hydrocarbonoclasticus strain 617), growing under aerobic conditions. The cultures with n-alkanes, as compared with soluble carbon sources, led to greater amounts of saturated and methyl branched FA (mainly belonging to a delta10 series). We observed the appearance or increase of saturated and unsaturated FA with the same carbon chain length (CCL) as the n-alkane carbon source (maximum for n-alkane CCL corresponding to the 'range' of the de novo synthesized fatty acids). We also observed a strong control of the oddness/evenness of the CCL of the FA by the oddness/evenness of the n-alkane. A n-alkane utilization index, (saturated + branched)/monounsaturated fatty acids (SAFA + BFA/MUFA) enabled discriminating between soluble carbon sources and hydrocarbons.     

Effect of soil amendments on sorption and mobility of metribuzin in soils

Metribuzin (4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one), is weakly sorbed to soil therefore, leaches easily to lower soil profiles. Soil amendments play a significant role in the management of leaching losses of pesticides. Therefore, present study reports the effect of organic manure and fly ash amendments on metribuzin downward mobility in sandy loam soil columns. Application of animal manure [T-1(OM) and T-2(OM)] and fly ash [T-1(FA) and T-2(FA)] at 2.5% and 5.0% levels increased the metribuzin retention in the soil. Freundlich constant [K(f)(1/n)] values of metribuzin for treatments T-1(OM) and T-2(OM) were 0.70 and 1.11, respectively, which were significantly higher than the value (0.27) in natural soil (T-0). The respective values for treatments T-1(FA) and T-2(FA) were 1.80 and 4.61. Downward mobility of metribuzin was studied in packed soil columns [300 mm (l)x59 mm (i.d.)]. Both the amendments significantly reduced the downward mobility of metribuzin and affected breakthrough time and maximum concentration of metribuzin in the leachate. Leaching losses of metribuzin were decreased from 97% in natural soil (T-0) column to 64% [T-1(OM)] and 42% [T-2(OM)] for animal manure-amended columns and 26% [T-1(FA)] to 100% [T-2(FA)] for fly ash-amended columns, as metribuzin did not leach out of 5% fly ash-amended column. Study indicates that both animal manure and fly ash were quite effective in reducing the downward mobility of metribuzin in packed soil columns of a sandy loam soil.     

Synchronous-scan fluorescence spectra of Chlorella vulgaris solution

The characterization of the Chlorella vulgaris solution was carried out using synchronous-scan spectroscopy. The range of concentration of algae and Fe(III) in aqueous solutions were 5 × 10⁸–8 × 10⁹ cells l⁻¹ and 10–60 μM, respectively. Effective characterization method used was synchronous-scan fluorescence spectroscopy. The wavelength difference (Δλ) of 90 nm was maintained between excitation and emission wavelengths; 90 nm was found to be the best Δλ for effective characterization of Chlorella vulgaris solution with or without quencher species (e.g., Fe(III), humic acid (HA)) for the first time. The peak was observed at about EX 236.6 nm/EM 326.6 nm for synchronous-scan fluorescence spectra. The fluorescence quenching of algae in system of algae–Fe(III)–HA was studied using synchronous-scan spectroscopy for the first time. Fe(III) was clearly the effective quencher. The relationship between I₀/I (quenching efficiency) and c (concentration of Fe(III) added) was a linear correlation for the algae solution with Fe(III). Also, Aldrich humic acid was found to be an effective quencher. pH effect on synchronous-scan fluorescence intensity of algal solution with Fe(III) and/or HA was evident.     

Fluorescence behaviour of Zn and Ni complexes of humic acids from different sources

Conventional fluorescence spectroscopy in the excitation, emission and synchronous scan modes and three-dimensional fluorescence spectroscopy in the form of an excitation-emission matrix (EEM) of fluorescence intensity as a function of excitation and emission wavelengths have been applied to the study of three humic acids (HAs) extracted from soil (SHA), peat (PHA) and compost (CHA) and their interaction products with Zn(II) and Ni(II) ions. Fluorescence spectra of HAs appear to be related to the nature and origin of the sample. A strong reduction of intensity of all peaks is observed in the spectra of HAs-metal complexes as compared to those of untreated HAs. Ni(II) exhibits greater quenching ability than Zn(II). Fluorescence quenching measured for complexes of HAs at increasing Ni(II) concentrations was linearly correlated with metal ion concentration. The different capacity to interact with metal ions showed by various HAs is attributed to their different molecular complexity.     

Influence of the composition and removal characteristics of organic matter on heavy metal distribution in compost leachates

Compost leachates were collected to investigate the influence of the composition and removal of volatile fatty acids (VFAs), humic-like substances (HSs), and dissolved organic nitrogen (DON) on heavy metal distribution during the leachate treatment process. The results showed that acetic and propionic acids accounted for 81.3 to 93.84 % of VFAs, and that these acids were removed by the anaerobic-aerobic process. Humic- and fulvic-like substances were detected by excitation–emission matrix spectroscopy coupled with parallel factor analysis, and their content significantly decreased after the anaerobic and membrane treatments. DON in compost leachates ranged from 26.53 mg L^-1 to 919.46 mg L^-1, comprised of dissolved free amino acids and the protein-like matter bound to humic- and fulvic-like substances, and was removed by the aerobic process. Correlation analysis showed that Mn, Ni, and Pb were bound to VFAs and protein-, fulvic-, and humic-like substances in the leachates. Co was primarily bound to fulvic- and humic-like matter and inorganic sulfurs, whereas Cu, Zn, and Cd interacted with inorganic sulfur.     

Spectroscopic studies of the progress of humification processes in humic substances extracted from refuse in a landfill

Humic acids (HA) and fulvic acids (FA) extracted from refuse in a landfill at different landfill ages were characterized by elemental composition, GPC, FTIR, and (13)C CP/MAS NMR. The elemental composition analysis revealed high O/C and low H/C ratios in the FA, indicating a high proportion of O-alkyl and carboxylic acids in the FA. The M(w) and M(n) values and M(w)/M(n) ratios indicated that the HA had a higher molecular weight and were more homogeneous with respect to molecular weight. FTIR spectra showed that the FA had relatively more intense bands assigned to aliphatic structures and were abundant in oxygen-containing function groups. The analytical results of (13)C CP/MAS NMR suggested that there were more oxygenated aliphatic carbons and fewer aromatic carbons in the FA than in the HA. All the results demonstrated that the degree of humification increased with landfill age.