城市污水生化处理后水中溶解性有机物的特性研究

采用XAD树脂分离技术和超滤膜法对青岛市某城市污水处理厂生物化学处理后出水中溶解性有机物（DOM）进行了分类分离,研究了出水中DOM的亲疏水特性及分子量分布规律,探讨了各类DOM组分与芳香度之间的关系.研究结果表明,在DOM中,酸性物质（包括过渡亲水酸性物质和疏水酸性物质）所占比例最高,占总溶解性有机碳（DOC）的79.8%,疏水非酸性物质的芳香度最高,并依疏水酸性物质、过渡亲水酸性物质、亲水性物质的顺序递减,且羰基、羧基、羟基、脂类对芳环的取代程度表现为亲水性物质〈过渡亲水酸性物质〈疏水非酸性物质〈疏水酸性物质;该污水处理厂二级出水中的DOM以小分子量有机物（相对分子质量小于1kDa）为主,其占总DOC的59.13%,表明水中腐殖酸类等难降解有机物质含量较高,增加了消毒副产物的生成势.因此,若该种水体需要深度处理时,应重点考虑提高对腐殖酸类等难降解有机物质的处理程度,确保回用水水质的安全性.     

Insight into the heavy metal binding potential of dissolved organic matter in MSW leachate using EEM quenching combined with PARAFAC analysis

Dissolved organic matter (DOM) plays an important role in heavy metal migration from municipal solid waste (MSW) to aquatic environments via the leachate pathway. In this study, fluorescence excitation-emission matrix (EEM) quenching combined with parallel factor (PARAFAC) analysis was adopted to characterize the binding properties of four heavy metals (Cu, Pb, Zn and Cd) and DOM in MSW leachate. Nine leachate samples were collected from various stages of MSW management, including collection, transportation, incineration, landfill and subsequent leachate treatment. Three humic-like components and one protein-like component were identified in the MSW-derived DOM by PARAFAC. Significant differences in quenching effects were observed between components and metal ions, and a relatively consistent trend in metal quenching curves was observed among various leachate samples. Among the four heavy metals, Cu(II) titration led to fluorescence quenching of all four PARAFAC-derived components. Additionally, strong quenching effects were only observed in protein-like and fulvic acid (FA)-like components with the addition of Pb(II), which suggested that these fractions are mainly responsible for Pb(II) binding in MSW-derived DOM. Moreover, the significant quenching effects of the FA-like component by the four heavy metals revealed that the FA-like fraction in MSW-derived DOM plays an important role in heavy metal speciation; therefore, it may be useful as an indicator to assess the potential ability of heavy metal binding and migration.     

Dissolved organic matter and the dissipation of chlorine in estuarine water and seawater

Dissolved organic matter in estuarine water and seawater collected in the summers of 1980 and 1981 in the James River, Virginia and the mouth of Chesapeake Bay were separated into fractions according to their nominal molecular weights (NMW) by ultrafiltration. Estuarine waters contained higher concentrations of dissolved organic carbon (DOC). Among the fractions, between 66–89% of the DOC was found in the fraction with NMW below 10,000. Estuarine waters also had higher chlorine demands. At a dose of 5 mg l⁻¹, in 23 h, about 90% of the added chlorine disappeared in estuarine waters, whereas, in seawater, only 60–75% of the chlorine had dissipated. At least two-thirds of the chlorine demand occurred in the first 5 h. About 10–30% of the chlorine demand may be attributed to the fraction with NMW above 10,000. The remaining chlorine demand was distributed almost equally between the fractions with ranges of NMW of 1000–10,000 and below 1000. If reactivity is measured in terms of organic chlorine demand (ΔClo) per unit weight of DOC, the fractions with lower NMW (< 1000 and 1000–10,000) always had a higher reactivity towards chlorine. Between these two fractions, the one with NMW between 1000 and 10,000 exhibited higher reactivity more frequently. The highest reactivity found was 1.4 mg ΔClo mg⁻¹ DOC.     

Screening of organic matter in leachates from sanitary landfills using gas chromatography combined with mass spectrometry

Sanitary landfills are potential groundwater pollution sources, normally producing leachate with very high content of organic matter. Leachates from five Danish sanitary landfills were sampled in order to investigate the composition of the organic matter. The samples were extracted using dichloromethane followed by sodium hydroxide solution, in this way dividing the sample into one phase containing the basic and neutral compounds and one containing the acidic compounds. One of the leachates was extracted using pentane, for analysis of volatile compounds. The three extracts were analysed using gas chromatography combined with mass spectrometry. Several compounds were identified, including chlorinated pesticides (2 of the 5 leachates), aromatic carboxylic acids and alkylbenzenes. Benzene, toluene and trichloroethylene were found in the leachate analysed for volatile compounds. Some of the compounds identified in this work have been reported in the literature to give rise to severe groundwater problems.     

Dissolved organic matter (DOM) in recycled leachate of bioreactor landfill

Landfill leachate needs sufficient treatment before safe disposal. Bioreactor landfill technology could effectively degrade the organic matters in recirculated leachate, hence leaving a leachate stream of low biodegradability. This study characterized the dissolved organic matter (DOM) in the leachate from simulated bioreactor landfill columns with or without presence of trace oxygen. The removal efficiencies of this DOM using coagulation-sedimentation or electrolysis processes were demonstrated. Recirculated leachates were sampled from the simulated landfill columns applying conventional mode, intermittent-aeration mode, and natural aeration mode, whose DOM was fractionated into humic acids (HA), fulvic acids (FA) and hydrophilic fractions (HyI) by the XAD-8 resin combined with the cation exchange resin method. The recirculated leachate had low BOD/COD ratio, high humic substances contents, and high aromatic content. Their HA fraction comprised mainly large molecules (>10 k Da), while the FA and HyI were composed of smaller molecules (<50 k and <4 k Da, respectively). With the presence of oxygen, the TOC contents and the contents of HA, FA and HyI in leachate reduced, with FA and HyI fractions of molecular weight (MW) lower than 4 k Da more readily degraded. The organic matters left in leachates from intermittent-aeration mode and natural aeration mode were of low biodegradability. It was tested in the following sections the effects of coagulation-sedimentation process and of electrolysis process on the removal of residual DOM in recirculated leachate. Coagulation-sedimentation tests revealed that poly ferric sulphate (PFS) could remove more COD (58.1%) from leachate than polyaluminum chloride (PACl) (22.9%), particularly on the HA fraction with MW>10 k Da. Coagulation-sedimentation could not remove most of HyI in leachate. Furthermore, the corresponding BOD/COD ratio was not improved through coagulation. Electrolysis test could also effectively removed HA of MW>10 k Da. However, the biodegradability of treated effluent considerably was improved. The electrolysis could decompose high MW substances and increase biodegradability of recirculated leachate from bioreactor landfill.     

Characterization of dissolved organic matter in drinking water sources impacted by multiple tributaries

The characterization of dissolved organic matter (DOM) in drinking water sources is important as this material contributes to the formation of disinfection by-products (DBPs) and affects how water treatment unit operations are optimized. Drinking water utilities often draw water from sources impacted by multiple tributaries, with possible shifts in DOM concentrations and reactivity over time, depending on specific environmental conditions. In this study, results are presented on the characterization of DOM under varying ambient conditions from the four main tributaries of Lake Mead, a large reservoir in the southwest United States. The tributaries include the Las Vegas Wash (LVW), Muddy River (MR), Virgin River (VR) and the upper Colorado River (UCR). One additional sample was collected at the outflow of the reservoir (lower Colorado River (LCR)). The DOM was characterized by both bulk parameters (specific ultraviolet absorbance (SUVA)) and specific physicochemical properties, i.e. size, polarity and fluorescence. The analyses were performed emphasizing limited changes in its natural configuration by eliminating analytical preparation steps, excluding sample filtration (0.45 microm filter). Results indicate that each tributary had a different molecular weight distribution, as well as fluorescence properties, which helped in the identification of the relative source of DOM (allochthonous versus autochthonous). The largest apparent molecular weight distribution was observed for DOM samples collected at the MR site, which is fed mostly by groundwater seepage. The smallest apparent molecular weight was observed for DOM collected at the LCR site, suggesting that retention in the reservoir resulted in a decrease in molecular weight as a probable result of photo oxidation and microbial processes. Fluorescence analysis aided the differentiation of DOM by clearly identifying waters that were affected by microbial activity (LVW, UCR, and LCR), either by wastewater influence or by autochthonous processes, versus limited microbial influence (MR and VR). Polarity analysis revealed clear differences in the hydrophobic/hydrophilic nature between waters, including temporal differences within individual waters at a particular site. The DOM from the LVW and VR sites had higher hydrophobic character, as measured by retention onto non-polar sorbents. Additionally, the DOM collected at the LCR had the least hydrophobic character. This type of analysis would be beneficial to utilities who want to better understand and manage their source waters, especially in the evaluation of temporal variation within a watershed.     

溶解性有机物的膜污染倾向沿程解析

近年来膜生物反应器(MBR)工艺的工程应用日益增多,溶解性有机物(DOM)作为重要的膜污染物质引起了广泛的关注.采用化学分析法和荧光光谱法(EEM)研究了DOM的组分含量和荧光特性的沿程变化,并应用膜过滤装置对DOM的膜污染倾向进行分析.结果表明,在生物降解、胞外聚合物释放及膜截留的综合作用下,DOM的各组分均表现出相似的变化趋势.其中,蛋白质和腐殖酸与膜污染指数(MFI)的相关性显著,R2分别为0.77和0.82,可能与污染物的浓度及分子质量有关.     

Removal and transformation of recalcitrant organic matter from stabilized saline landfill leachates by coagulation-ozonation coupling processes

The Bordo Poniente sanitary landfill in Mexico City currently receives 11,500 ton/day of solid wastes. The landfill has been in operation since 1985, in what was formerly Texcoco Lake, now a dried-up lakebed. The physico-chemical characteristics of the leachate generated by this particular landfill are altered by the incorporation of freatic saline water present in the area. This paper reports the results from a study evaluating coagulation and ozonation as alternative processes for removing and transforming recalcitrant organic matter from stabilized saline landfill leachate. Coagulation with ferric sulfate was found to remove up to 67% of COD and 96% of leachate color. The remaining 33% COD was removed with ozone. Recalcitrant organic matter removal by ozonation is limited by the reaction kinetic due mainly to ozone's low reactivity with the organic compounds present in the leachates (amines, amides, alcohols, aliphatic compounds, and carboxylic acids). However, ozone contributes greatly to changing the recalcitrant characteristics of organic matter. Leachate biodegradability was found to be significantly enhanced through ozonation: BOD(5) values reach 265%, and the BOD(5)/COD ratio increases from 0.003 to 0.015. Infrared analysis of ozonated leachates shows that the main by-products of recalcitrant organic matter ozonation are an increase in the hydroxyl and carboxylic groups, and the presence of aldehydes groups.     

农家乐污水中溶解性有机质的三维荧光特性研究

采用三维荧光光谱(3DEEM)技术考察了农家乐污水中溶解性有机质的三维荧光特性.结果表明,农家乐污水中的有机污染物荧光峰以类蛋白质荧光峰为主,其中高激发波长类色氨酸荧光峰Peak T最强,其次是低激发波长类色氨酸荧光峰Peak S和低激发波长类酪氨酸荧光峰Peak D;综合性农家乐污水的Peak S和Peak D荧光强度比以餐饮为主的农家乐污水的要强.农家乐污水经受纳水体稀释和净化后,类蛋白质荧光强度仍远高于地表水的.其对受纳水体的污染不容忽视.     

Characterization of dissolved organic matter in a submerged membrane bioreactor by using three-dimensional excitation and emission matrix fluorescence spectroscopy

Three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy was employed to characterize dissolved organic matter (DOM) in a submerged membrane bioreactor (MBR). Three fluorescence peaks could be identified from the EEM fluorescence spectra of the DOM samples in the MBR. Two peaks were associated with the protein-like fluorophores, and the third was related to the visible humic acid-like fluorophores. Only two main peaks were observed in the EEM fluorescence spectra of the extracellular polymeric substance (EPS) samples, which were due to the fluorescence of protein-like and humic acid-like matters, respectively. However, the EEM fluorescence spectra of membrane foulants were observed to have three peaks. It was also found that the dominant fluorescence substances in membrane foulants were protein-like substances, which might be due to the retention of proteins in the DOM and/or EPS in the MBR by the fine pores of the membrane. Quantitative analysis of the fluorescence spectra including peak locations, fluorescence intensity, and different peak intensity ratios and the fluorescence regional integration (FRI) analysis were also carried out in order to better understand the similarities and differences among the EEM spectra of the DOM, EPS, and membrane foulant samples and to further provide an insight into membrane fouling caused by the fluorescence substances in the DOM in submerged MBRs.     

Characterisation of dissolved organic matter in karst spring waters using intrinsic fluorescence: relationship with infiltration processes

From analysis of spectrophotometric properties of dissolved organic matter (OM) and the hydrochemical responses of some karst springs under different hydrologic conditions, an assessment of the origin and transfer pathway of OM present in karst spring waters, from soil and epikarst toward the spring, has been conducted for three karst aquifers in southern Spain: Alta Cadena, Sierra de Enmedio and Los Tajos. Intrinsic fluorescence (excitation-emission matrices or EEMs), together with major water chemistry (electrical conductivity, temperature, alkalinity, Cl⁻, Mg^+ 2) and P_CO2 along with natural hydrochemical tracers (TOC and NO₃⁻), have been monitored in 19 springs which drain the three karst aquifers examined in this study. The spring water EEM spectra indicate that fulvic acid-like substances, produced in the soil as a consequence of the decomposition of OM, are the dominant fluorophores, although some of the OM appears to originate from in situ microbiological activity but could be indicative of contamination present in recharge waters from livestock. During each recharge event, TOC and NO₃⁻ concentrations increased and variations in fluorescence intensities of peaks attributed to fulvic acid-like compounds were observed. In areas with minimal soil development, spatial and temporal variations in the fluorescence intensity of fulvic acid-like substances and other fluorophores derived from microbiological activity, together with other hydrochemical parameters, provide insights into the hydrogeological functioning of karst aquifers and the infiltration velocity of water from soil and facilitate assessment of contamination vulnerability in these aquifers.     

Isolation of dissolved organic matter from the suwannee river using reverse osmosis

A portable reverse osmosis (RO) system was constructed and used to concentrate dissolved organic matter (DOM) from the Suwannee River in southeastern Georgia. Using this RO system, 150–180 1/h of river water could be processed with 90% recovery of DOM. After further cation exchange and lyophilization of the concentrated river water samples, large quantities of low-ash freeze-dried products were isolated. We highly recommend this RO method for concentration of DOM in fresh waters because (1) a very high percentage of DOM is recovered, which indicates minimal fractionation of the original sample; and (2) the process is quite rapid, which permits large quantities of DOM to be concentrated in a reasonable length of time.     

Comparison of river and canal water dissolved organic matter fluorescence within an urbanised catchment

Recently, growing interest has been shown in the study of canal water quality, yet no research using continuous fluorescence monitoring to characterise dissolved organic matter (DOM) has been performed. This paper evaluated DOM characteristics at hourly resolution. A comparison was made between canal and nearby urban river fluorescence spectra, to emphasise the specific nature of canal water DOM. Results showed that canal water had a significant proportion of microbially derived DOM, while the urban river had a greater proportion of terrestrially derived fractions. The microbial character of canal water DOM originated from the low flow of water, the nutrients predominance and continuous DOM processing. Hence, DOM fluorescence is invariant over a timescale of days, and recreational navigation and precipitation events have no major influence on DOM characteristics. Our results are expected to be applicable to future research on highly regulated freshwater systems for DOM quantity estimation or for water quality models.     

UV-induced photochemical heterogeneity of dissolved and attached organic matter associated with cyanobacterial blooms in a eutrophic freshwater lake

Cyanobacterial blooms represent a significant ecological and human health problem worldwide. In aquatic environments, cyanobacterial blooms are actually surrounded by dissolved organic matter (DOM) and attached organic matter (AOM) that bind with algal cells. In this study, DOM and AOM fractionated from blooming cyanobacteria in a eutrophic freshwater lake (Lake Taihu, China) were irradiated with a polychromatic UV lamp, and the photochemical heterogeneity was investigated using fluorescence excitation–emission matrix (EEM)-parallel factor (PARAFAC) analysis and synchronous fluorescence (SF)-two dimensional correlation spectroscopy (2DCOS). It was shown that a 6-day UV irradiation caused more pronounced mineralization for DOM than AOM (59.7% vs. 41.9%). The EEM-PARAFAC analysis identified one tyrosine-, one humic-, and two tryptophan-like components in both DOM and AOM, and high component photodegradation rates were observed for DOM versus AOM (k > 0.554 vs. <0.519). Moreover, SF-2DCOS found that the photodegradation of organic matters followed the sequence of tyrosine-like > humic-like > tryptophan-like substances. Humic-like substances promoted the indirect photochemical reactions, and were responsible for the higher photochemical rate for DOM. The lower photodegradation of AOM benefited the integrality of cells in cyanobacterial blooms against the negative impact of UV irradiation. Therefore, the photochemical behavior of organic matter was related to the adaptation of enhanced-duration cyanobacterial blooms in aquatic environments.     

Effects of mass retention of dissolved organic matter and membrane pore size on membrane fouling and flux decline

Ultrafiltration (UF) fouling has been attributed to concentration polarization, gel layer formation as well as outer and inner membrane pore clogging. It is believed that mass of humic materials either retained on membrane surface or associated with membrane inner pore surface is the primary cause for permeate flux decline and filtration resistance build-up in water supply industries. While biofilm/biofouling and inorganic matter could also be contributing factors for permeability decline in wastewater treatment practices. The present study relates UF fouling to mass of dissolved organic matter (DOM) retained on membrane and quantifies the effect of retained DOM mass on filtration flux decline. The results demonstrate that larger pore membranes exhibit significant flux decline in comparison with the smaller ones. During a 24-h period, dissolved organic carbon mass retained in 10 kDa membranes was about 1.0 g m⁻² and that in 100 kDa membranes was more than 3 times higher (3.6 g m⁻²). The accumulation of retained DOM mass significantly affects permeate flux. It is highly likely that some DOMs bind or aggregate together to form surface gel layer in the smaller 10 kDa UF system; those DOMs largely present in inner pore and serving as pore blockage on a loose membrane (100 kDa) are responsible for severe flux decline.     

Reduction of dissolved organic matter and trihalomethane formation potential during laboratory-scale soil-aquifer treatment

Dissolved organic matter (DOM) in recovered groundwater from soil-aquifer treatment (SAT) has the potential to generate harmful disinfection by-products. This study investigated the reduction of mass and trihalomethane formation potential (THMFP) of DOM fractions from secondary effluent during laboratory-scale SAT. Using XAD-8 and XAD-4 resins, DOM was fractionated into three fractions: hydrophobic acid (HPO-A), transphilic acid (TPI-A) and hydrophilic fraction (HPI). HPO-A was removed by 61.1%, TPI-A by 54.9% and HPI by 75.0% as dissolved organic carbon (DOC) during the laboratory-scale SAT, respectively. The reduction of THMFP from HPO-A, TPI-A and HPI was 27.24, 26.24 and 36.08%, respectively. Specific THMFP for each DOM fraction increased across the soil columns. HPO-A was found to be the major precursor of THMs. THMFP was strongly correlated to ultraviolet light at 254 nm (UV-254) for HPO-A and HPI, while the relationship between THMFP and UV-254 for TPI-A was significantly poor.     

Identification of organic compounds in leachate from a waste tip

Two different types of leachate from a municipal waste tip have been analyzed. The first type of leachate was collected from a waste tip in the acidification stage. The organic load of this leachate was high and consisted mainly of free volatile acids (over 95% of the TOC). Volatile amines and ethanol were also present (0.8 and 0.7% of the TOC respectively). The leachate was extracted with hexane and the extract was analyzed with infrared and nuclear magnetic resonance spectroscopy and a gas chromatograph-mass spectrometer combination. In the extract alcohols, hydrocarbons, esters, terpenes and phthalates have been identified. High molecular weight compounds were present only in a low concentration.The second type of leachate was collected from a waste tip in the methane fermentation stage. The organic load was relatively low. An important part of the organics was identified as high molecular weight compounds. About 32% of the organic carbon consisted of compounds with a molecular weight over 1000. Acids, amines and alcohols could not be detected. This means that the organic compounds present were end products of degradation processes.Furthermore there was a remarkable difference in heavy metal content between the two types of leachate.     

垃圾渗滤液在不同介质中迁移转化规律

在实验室中,通过土柱对比实验研究了渗滤液污染组分总氮、TOC在不同介质中的迁移转化规律。实验结果表明：砂土对总氮、TOC的衰减率大于细砂对其衰减量,咸水对地下环境中总氮、TOC的衰减率有阻碍作用。     

Fractionation of dissolved organic matter from surface waters using macroporous resins

To obtain fractions enriched with biodegradable dissolved organic carbon (BDOC) or with organic compounds responsible for the chlorine demand (CID) and for trihalomethane formation potential (THMFP), Seine river water samples were percolated on various macroporous resins (anionic, cationic and non-ionic) and compared with granulated activated carbon (GAC). In addition, measurement of UV absorbance at 254 nm and the fluorescence index (λ_excitation 320 nm) had allowed to follow up the retention of dissolved organic matter by the different adsorbants. In contrast to cationic and non-ionic resins, anionic resins confirm their excellent retention capacity of organic compounds responsible for UV 254 absorbance and fluorescence index. The relative values of BDOC/DOC ratio (mg-C/mg-C) are slightly increased in the effluents of anionic resins, indicating that they retain a little preferentially the refractory fraction instead of the biodegradable fraction. There is no significant difference between the ratio of CID/DOC (mg-Cl₂/mg-C) in influent and effluent of anionic resins. Cationic resin has a low capacity for retention of DOC, but they seem to retain significantly the organic compounds responsible for CID. The capability of anionic resins to retain THMFP is similar to that of GAC.     

Heterogeneity of natural organic matter from the Chena River,Alaska

Water samples were collected in July 2001 from the Chena River in central Alaska. The natural organic matter (NOM) was size fractionated into particulate (POM,>0.45 microm), colloidal (COM,1kDa-0.45 microm) and dissolved (DOM,<1k Da) organic matter fractions, using filtration and ultrafiltration. The size-fractionated organic matter was then analyzed for organic carbon (OC) and nitrogen (N), isotopic (delta13C and delta15N) and molecular composition, using continuous flow isotope ratio mass spectrometry and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Results of phase partitioning showed that, on average, about 6% of OC and 16% of N occurred in the form of POM while 66% of OC and 57% of N occurred in the form of COM, and 28% of the OC and 27% of the N were in the DOM form. Organic matter in the river water was found to be highly heterogeneous in terms of chemical composition and isotopic signatures. The C/N ratio was as low as 16+/-1 in the POM (n=2) to as high as 48+/-1 in the COM (n=3) and 38+/-4 in the DOM (n=3), suggesting a diagenetically younger POM. Values of delta13C increased with decreasing size, varying from -29.59+/-0.45% in the POM to -27.47+/-0.06% in the COM to -16.93+/-0.08% in the DOM. In contrast, values of delta15N decreased with decreasing size, from 2.64% in POM to 1.64% in COM to 1.33% in DOM. These results, together with radiocarbon measurements, suggest a preferential decomposition of lighter C isotope (12C) and heavier N isotopic (15N) from POM to COM to DOM. Results of py-GC/MS showed that the percentage of polysaccharides decreased with decreasing size, further supporting a degradation pathway of NOM from POM to COM and DOM in Chena River waters. More studies are needed to examine the seasonal and spatial variations of size-fractionated organic matter.