炼油厂达标废水中溶解性有机物的表征

采用超滤和凝胶色谱法调查了炼油厂达标废水中溶解性有机物 (DOM)的分子量分布 ,并用树脂吸附和离子交换技术研究了该废水DOM中疏水性酸 (HoA)、碱 (HoB)及中性物 (HoN)和亲水性酸 (HiA)、碱 (HiB)及中性物 (HiN)的比例 ,用气相色谱 质谱法 (GC MS)定性分析了疏水性有机物的组成 .结果表明 ,某炼油厂达标废水的TOC为 12 0 6～ 16 80mg·L-1,其中溶解性有机碳 (DOC)为 10 15～ 14 4 4mg·L-1;分子量 <1k的DOM约为 80 % (以TOC计 ) ;DOM中HiN、HoN、HoA、HiB、HoB及HiA的含量分别为 2 9 7% ,2 6 5 % ,2 1 1% ,13 4 % ,5 1%及 4 2 % .鉴定出的HoN包括脂肪烃、苯系物、含硫化合物及邻苯二甲酸酯类化合物等 ,其中C10和C11脂肪烃、甲基亚硫酰苯及邻苯二甲酸二丁脂化合物的含量相对较高 .根据表征结果提出了回用处理建议.     

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。     

皂素废水处理过程中有机物变化的表征

通过比较皂素废水、内电解、好氧与厌氧处理后废水中有机物质的分子量分布以及组成特点,确定皂素废水处理过程中有机物的变化。结果表明:厌氧与好氧处理后,COD值有显著减少;皂素废水经过厌氧和好氧处理后还生成一些新物质,微生物产物(SMP)。     

呼伦湖水体溶解性有机物荧光特征及来源分析

呼伦湖是我国北方生态安全屏障的重要组成部分,为探究呼伦湖水体中有机物的组成及来源,利用三维荧光光谱（EEMs）结合平行因子（PARAFAC）分析技术进行溶解性有机物（DOM）荧光特征及来源研究。结果表明：呼伦湖DOM中含有3种荧光组分,分别为类色氨酸（C1）、类腐殖酸（C2）和类富里酸（C3）;平水期、丰水期和枯水期的C2和C3荧光强度占比约70%,表明呼伦湖水体DOM以腐殖质类物质为主,其中不同水期生态补水工程入湖口的C2和C3荧光强度均高于其他区域;平水期、丰水期和枯水期的荧光指数、生物指数和腐殖化指数平均值分别为1.50~1.54、0.85~1.00和4.12~4.68,表明呼伦湖DOM由陆源和自生源混合组成,具有明显的自生源特征;水质监测数据表明,2021年呼伦湖平水期、丰水期和枯水期水质均为GB 3838—2002《地表水环境质量标准》劣Ⅴ类,其中平水期和丰水期的BOD₅平均值高于枯水期,而平水期总有机碳平均浓度高于丰水期和枯水期;不同水期C2和C3的荧光强度均呈显著正相关,表明DOM中组分C2和C3的产生及来源具有一致性。

     

地下水中溶解性有机物的季节变化特征及成因

为阐明地下水中溶解性有机物(DOM)的分布特征与环境效应,联合三维荧光光谱、平行因子分析及主成分分析,研究了地下水中DOM的来源及随季节和空间变化特征,探究了地下水DOM组成对无机盐分布的影响.结果显示,地下水DOM主要来自微生物源,可鉴别出4种荧光组分,4种组分中,组分1和3为类蛋白组分,组分2和4属于类腐殖质组分.类蛋白组分来源差异较大,组成不稳定,其含量随季节变化明显,春冬季含量低而夏秋季含量高;类腐殖质组分来源相似,组成稳定,随季节变化小.两类荧光组分,尤其是类蛋白组分,是地下水氨氮的主要来源,可以影响地下水pH值.结果表明,三维荧光光谱结合平行因子和主成分分析,可以解析地下水中有机物的组成特征和季节变化规律.     

垃圾渗滤液中溶解性有机物对土壤重金属吸附

垃圾渗滤液主要组分为重金属和大量的溶解性有机物(DOM). 选取我国北方具有代表性的褐土,通过不同pH(5～9)和温度 (15,25和35 ℃)下的等温吸附试验,研究了垃圾渗滤液中DOM对Cu, Cd, Pb和Zn 4种重金属在土壤中吸附行为的影响. 结果表明:DOM对Cu和Cd在土壤中的吸附促进作用较明显,对Pb有微弱的促进作用,对Zn的吸附影响不明显;改变pH,DOM对4种重金属在褐土中的吸附也表现出不同的影响,吸附平衡后土壤溶液pH变化差异明显;25 ℃下Cu在土壤中的吸附量高于15和35 ℃条件下;有DOM时,Cd, Zn和Pb在土壤中的吸附量随着温度的升高而增大.      

腈纶废水溶解性有机物的分级解析及可生化性

采用超滤膜法将腈纶废水中溶解性有机物分离为6个不同相对分子质量组分,分析不同组分的溶解性有机碳、UV₂₅₄、SUVA含量和分布情况,应用紫外吸收光谱、傅里叶变换红外光谱等光谱学分析方法对各组分物质结构进行定性分析,评价各组分的可生化性.结果表明废水中以相对分子质量< 3kDa的有机物为主,占比为（56.75±1.38）%;相对分子质量为3k~10kDa的有机物占比为（25.76±1.40）%;相对分子质量> 10kDa的有机物占比为（17.49±0.98）%,且该组分有机物的芳香度高.不同相对分子质量组分的紫外光谱和红外光谱均呈现相似吸收峰,均存在酰基、羧基、羰基及芳香族化合物和不饱和双键类有机物.各组分可生化性结果表明,废水中相对分子质量> 10kDa有机物是腈纶废水低可生化性的主要原因,可能是造成腈纶废水难以达标排放的根源.研究结果可为该废水处理工艺的开发与优化提供重要的指导.     

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.     

地下水中溶解性有机物的垂直分布特征及成因

地下水中溶解性有机物(DOM)能够改变外来污染物的存在形态和迁移转化过程,其组成和分布特征研究具有重要的环境意义.采用紫外-可见吸收光谱和荧光光谱,联合平行因子分析和主成分分析,对3个不同埋深(1.2、1.5及1.8 m)地下水中DOM的来源、组成、浓度、分布特征及影响因素进行了研究,结果表明,地下水中DOM来源于陆源有机质输入和微生物活动,含有类腐殖质、异质性有机物和类蛋白物质这3种组分,类腐殖质与异质性有机物在中下层含量最高而表层最低,类蛋白物质在中间层含量最低而表层含量最高.中下层地下水中DOM的芳香性、腐殖化率、分子量和极性官能团含量最高,而表层地下水中DOM的芳香性、腐殖化率、分子量和极性官能团含量最低.地下水中DOM的垂直分布主要受有机质腐殖化率、芳香性、分子量和极性影响,腐殖化率和芳香性强、分子量大和极性高的DOM难降解、易迁移进入下层地下水.     

Diverse molecular compositions of dissolved organic matter derived from different composts using ESI FT-ICR MS

Dissolved organic matter (DOM) derived from various composts can promote significant changes of soil properties. However, little is known about the DOM compositions and their similarities and differences at the molecular level. In this study, the molecular compositions of DOM derived from kitchen waste compost (KWC), green waste compost (GWC), manure waste compost (MWC), and sewage sludge compost (SSC) were characterized by electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The molecular formulas were classified into four subcategories: CHO, CHON, CHOS, and CHONS. The KWC, MWC, and SSC DOM represented the highest fraction (35.8%-47.4%) of CHON subcategory, while the GWC DOM represented the highest fraction (68.4%) of CHO subcategory. The GWC DOM was recognized as the nitrogen- and sulfur-deficient compounds that were less saturated, more aromatic, and more oxidized compared with other samples. Further analysis of the oxygen, nitrogen-containing (N-containing), and sulfur-containing (S-containing) functional groups in the four subcategories revealed higher organic molecular complexity. Comparison of the similarities and differences of the four samples revealed 22.8% ubiquitous formulas and 17.4%, 11.1%, 10.7%, and 6.3% unique formulas of GWC, KWC, SSC, and MWC DOM, respectively, suggesting a large proportion of ubiquitous DOM as well as unique, source-specific molecular signatures. The findings presented herein provide new insight into the molecular characterization of DOM derived from various composts and demonstrated the potential role of these different compounds for agricultural utilization.     

Characterisation of dissolved organic matter in stormwater using high-performance size exclusion chromatography

Understanding the complexity of dissolved organic matter(DOM)in stormwater has drawn a lot of interest,since DOM from stormwater causes not only environmental impacts,but also worsens downstream aquatic quality associated with water supply and treatability.This study introduced and employed high-performance size exclusion chromatography(HPSEC)coupled with an ultraviolet–visible(UV–vis)diode array detector to assess changes in stormwater-associated DOM characteristics.Stormwater DOM was also analysed in relation to storm event characteristics,water quality and spectroscopic analysis.Statistical tools were used to determine the correlations within DOM and water quality measurements.Results showed that dissolved organic carbon(DOC)and UV absorbance at 254 nm(UV_(254))as conventional DOM parameters were found to be correlated well to the changes in stormwater quality during each of the three storm events studied.Both detector wavelengths(210and 254 nm)and their ratio(A_(210)/A_(254))were found to provide additional information on the physiochemical properties of stormwater-associated DOM.This study indicated that A_(210)/A_(254) is an important parameter which could be used to estimate the DOM proportions of functional groups and conjugated carbon species.This study provided also an understanding of stormwater quality constituents through assessing variability and sensitivity for various parameters,and the additional information of rainfall characteristics on runoff quality data for a better understanding of parameter correlations and influences.     

Characterization of dissolved organic matter and membrane fouling in coagulation-ultrafiltration process treating micro-polluted surface water

Coagulation–ultrafiltration(C–UF) is widely used for surface water treatment. With the removal of pollutants, the characteristics of organic matter change and affect the final treatment efficiency and the development of membrane fouling. In this study, we built a dynamic C–UF set-up to carry out the treatment of micro-polluted surface water, to investigate the characteristics of dissolved organic matter from different units. The influences of poly aluminum chloride and poly dimethyldiallylammonium chloride(PDMDAAC) on removal efficiency and membrane fouling were also investigated. Results showed that the dosage of PDMDAAC evidently increased the UV254 and dissolved organic carbon removal efficiencies,and thereby alleviated membrane fouling in the C–UF process. Most hydrophobic bases(HoB)and hydrophobic neutral fractions could be removed by coagulation. Similarly, UF was good at removing HoB compared to hydrophilic substances(HiS) and hydrophobic acid(HoA)fractions. HiS and HoA fractions with low molecule weight accumulated on the surface of the membrane, causing the increase of transmembrane pressure(TMP). Membrane fouling was mainly caused by a removable cake layer, and mechanical cleaning was an efficient way to decrease the TMP.     

Transport and humification of dissolved organic matter within a semi-arid floodplain

In order to understand the transport and humification processes of dissolved organic matter(DOM) within sediments of a semi-arid floodplain at Rifle,Colorado,fluorescence excitation–emission matrix(EEM) spectroscopy,humification index(HIX) and specific UV absorbance(SUVA) at 254 nm were applied for characterizing depth and seasonal variations of DOM composition.Results revealed that late spring snowmelt leached relatively fresh DOM from plant residue and soil organic matter down into the deeper vadose zone(VZ).More humified DOM is preferentially adsorbed by upper VZ sediments,while non-or lesshumified DOM was transported into the deeper VZ.Interestingly,DOM at all depths undergoes rapid biological humification process evidenced by the products of microbial by-product-like(i.e.,tyrosine-like and tryptophan-like) matter in late spring and early summer,particularly in the deeper VZ,resulting in more humified DOM(e.g.,fulvic-acid-like and humic-acid-like substances) at the end of year.This indicates that DOM transport is dominated by spring snowmelt,and DOM humification is controlled by microbial degradation,with seasonal variations.It is expected that these relatively simple spectroscopic measurements(e.g.,EEM spectroscopy,HIX and SUVA) applied to depth-and temporally-distributed pore-water samples can provide useful insights into transport and humification of DOM in other subsurface environments as well.     

氯化对二级处理出水中溶解性有机物荧光特性的影响

以哈尔滨市W污水处理厂为研究对象,利用XAD树脂对二级处理出水中的溶解性有机物(DOM)进行分级分离.按照DOM在不同树脂上的吸附特性将其分为5个部分:疏水性有机酸(HPO-A)、疏水性中性有机物(HPO-N)、过渡亲水性有机酸(TPI-A)、过渡亲水性中性有机物(TPI-N)和亲水性有机物(HPI).考察了DOM各组分在氯化过程中荧光特性的变化.研究结果表明,DOM中的类腐殖酸荧光物质、类溶解性微生物代谢产物荧光物质和类芳香族蛋白质荧光物质参与了氯化反应.此外,HPO-A、HPO-N、TPI-A和TPI-N中的类富里酸荧光物质,HPO-A、HPO-N和TPI-A中带有3～5个稠合苯环的芳香族化合物,以及HPO-N中的萘及其衍生物与氯反应.TPI-N和HPI与氯反应后,生成了具有多环芳香结构的荧光物质.HPI与氯反应后生成了类富里酸荧光团.各DOM组分与氯反应后,在激发波长为320nm的荧光发射光谱图上波长大于与该光谱图上最高荧光强度对应的波长的范围内,与最高荧光强度的一半等值的荧光强度相对应的波长变短,其中以TPI-N和HPI最为显著.而这种现象在激发波长为280nm和370nm的荧光发射光谱图却没有被观察到.     

煤矿区废水中溶解性有机质与铜的结合特性

为研究煤矿区废水排放对环境中重金属化学行为的影响,通过荧光滴定实验,利用铜离子选择电极法和荧光猝灭法定量化研究了矿井水和生活污水中溶解性有机质对铜的结合行为.结果表明,铜离子选择性电极法能精确地定量化这2类废水中有机质对铜的结合容量,其中矿井水中有机质对铜具有较大的结合容量,可以达到163.9mg/g,而生活污水中有机质对铜的结合容量相对较小,只有72.6mg/g.荧光猝灭法结果表征了这2类废水中各个组分对铜的结合特性,其中矿井水中的富里酸(A峰)对铜具有较强的结合容量,而生活污水中的类蛋白组分对铜的结合能力相对较弱.2类废水与铜结合前后的红外光谱变化结果表明矿井水中腐殖酸物质与铜的结合是一种化学反应,其中的酚羟基和羧基等官能团参与了反应,但生活污水中类蛋白物质的官能团与铜并没有发生化学结合反应.     

Molecular characterization of effluent organic matter in secondary effluent and reclaimed water: Comparison to natural organic matter in source water

Municipal wastewater reclamation is becoming of increasing importance in the world to solve the problem of water scarcity. A better understanding of the molecular composition of effluent organic matter(Ef OM) in the treated effluents of municipal wastewater treatment plants(WWTPs) is crucial for ensuring the safety of water reuse. In this study, the molecular composition of Ef OM in the secondary effluent of a WWTP in Beijing and the reclaimed water further treated with a coagulation–sedimentation–ozonation process were characterized using a non-target Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) method and compared to that of natural organic matter(NOM) in the local source water from a reservoir. It was found that the molecular composition of Ef OM in the secondary effluent and reclaimed water was dominated by CHOS formulas, while NOM in the source water was dominated by CHO formulas. The CHO formulas of the three samples had similar origins. Anthropogenic surfactants were responsible for the CHOS formulas in Ef OM of the secondary effluent and were not well removed by the coagulation-sedimentation-ozonation treatment process adopted.     

农业常用有机物料中水溶性有机物的理化性质特征

以水稻土水溶性有机物(DOM)为对照,采用物理化学和光谱学实验研究了农业上常用有机物料:猪粪、绿肥和污泥DOM的理化性质差异.结果表明,水稻土、污泥、猪粪和绿肥DOM含量分别为122, 23793, 12904, 380560mgC/kg.若施用等量有机物料,带入土壤的DOM量最多的应是绿肥.不同有机物料DOM中大分子组分含量高低顺序为:水稻土(51.08%)>猪粪(41.25%)>污泥(23.33%)>绿肥(7.36%);而极性组分含量的顺序则相反,水稻土(10.71%)猪粪DOM(1.12)>污泥DOM(1.11)>绿肥DOM(0.98),紫外图谱也证实了这一点.     

Occurrence, polarity and bioavailability of dissolved organic matter in the Huangpu River, China

Dissolved organic matter （DOM） plays an important role in biogeochemical cycles in aquatic ecosystem. To investigate the characteristics of DOM in Huangpu River {the last tributary of the Yangtze River）, surface water samples were collected along the river from December 2011 to June, 2013. The concentrations of dissolved organic carbon （DOC）, the absorbance and fluorescence spectrum of DOM in water samples were measured. Fluorescent DOM in the Huangpu River was decomposed into four components by the parallel factor analysis （PARAFAC）, including one humic-like substance and three protein-like substances. It showed that high spatial variability of DOC concentration was observed in the upstream water compared to the downstream water, and so did the absorbance coefficients of chromophoric dissolved organic matter and the total fluorescence intensities of different PARAFAC components of DOM. Furthermore, there was a large difference between the polarity and bioavailability of DOM in the Huangpu River. Polar compounds dominated tyrosine-like component of fluorescent DOM in all seasons. Tryptophan-like and humic-like substances had more polar fraction in summer and autumn than those in winter, while aromatic protein-like materials had the highest polar fraction in winter. Almost all of fluorescent DOM components were refractory in spring, while less than 20% of fluorescent DOM in average were biodegradable within 4 weeks in other seasons. We concluded that the spatial variation in the abundance of DOM in the Huangpu River is mainly affected by the water discharges from the Hangjiahu Plain and the seasonal difference in polarity and bioavailability of DOM is largely determined by its origins.     

The migration and transformation of dissolved organic matter during the freezing processes of water

This study investigated the partitioning behavior of dissolved organic matter (DOM) in liquid and ice phases, as well as the changes in the optical properties and chlorine reactivity of DOM during the freezing processes of water. DOM was rejected from the ice phase and accumulated in the remaining liquid phase during water freezing. Moreover, the decrease in freezing temperature, as well as the increase in dissolved organic carbon (DOC) concentration of feed water, caused an increase in DOM captured in the ice phase. The ultraviolet-absorbing compounds, trihalomethane precursors, as well as fulvic acid- and humic acid-like fluorescent materials, were more liable to be to be rejected from the ice phase and were more easily retained in the unfrozen liquid phase during water freezing, as compared with organics (on average) that comprise DOC. In addition, it was also found a higher accumulation of these organics in the unfrozen liquid phase during water freezing at higher temperature. The freeze/thaw processes altered the quantity, optical properties, and chlorine reactivity of DOM. The decrease in ultraviolet light at 254 nm as well as the production of aromatic protein- and soluble microbial byproduct-like fluorescent materials in DOM due to freeze/thaw were consistently observed. On the other hand, the changes in DOC, trihalomethane formation potential, and fulvic acid- and humic acid-like fluorescence caused by freeze/thaw varied significantly between samples.