水体溶解性有机物的化学分级表征:原理与方法

综述了水体溶解性有机物(DOM)的化学分级表征法即树脂吸附分级法(RA)的研究与进展,同时基于该方法存在的一些问题结合我国典型水质体系,从树脂的选择、净化、分级的定义、水样过柱流速、水样树脂体积比的确定等方面进行了研究探讨,给出了完整的实验参数和操作方法.     

河道藻源胞内有机质光化学-生物降解机制

藻细胞破裂后会向水体释放大量的胞内有机质 (intracellular dissolved organic matter, I-DOM) 。I-DOM在河道中将经历复杂的光降解和生物降解过程,影响其在河道中的迁移转化和环境效应。为了探明光照和微生物对I-DOM的降解机制,开展了光降解、生物降解和光-生物降解实验。结果表明,I-DOM经7 d光降解和生物降解后,溶解性有机碳 (dissolved organic carbon, DOC) 的去除率分别为70%和81%;虽然光照1 d能去除38%的DOC,但后续生物降解 (光-生物降解) 与无光照生物降解对DOC的去除效率一致。进一步的研究表明,生物降解过程中的呼吸商 (respiratory quotient, RQ) 低于光-生物降解过程,说明相比于生物降解过程,光-生物降解过程中经光照后生物呼吸时所利用I-DOM的性质发生了改变,进而影响了生物呼吸时O₂的消耗和CO₂的产生。生物降解过程中微生物主要利用原始的I-DOM分子;而在光-生物降解过程中,生物降解过程的微生物主要利用经光降解转化后的I-DOM分子。光-生物降解过程中,光照消耗了I-DOM中可生物降解的脂质、蛋白质和木质素类组分,导致I-DOM的生物降解效率降低;同时,光照将I-DOM中的大分子物质分解成高O/C的小分子物质,使微生物代谢需要的O₂减少,小分子物质则更易被生物降解矿化生成CO₂,导致RQ升高。本研究结果可为河道水质调控提供参考。     

Fenton法降解垃圾渗滤液中的溶解性有机质

垃圾渗滤液是一种高浓度难降解废水,含有大量有毒物质和溶解性有机质（dissolved organic matter, DOM）,可生化性差。Fenton试剂（Fe2++H2O2）能产生活性极强的羟基自由基（·OH）,能快速氧化渗滤液中DOM和微量有机物质。本研究采用Fenton法处理垃圾渗滤液,结果表明,在优化的处理条件下,渗滤液COD和TOC去除率分别为65%和42%,其中混凝作用去除的COD和TOC分别为20%和21%。进一步通过紫外可见光谱扫描、SUVA254、E3/E4等指标评价,发现Fenton法可以有效降低渗滤液中的DOM含量,大分子有机物的含量明显减少,而分子量小的有机物含量相对增加,反应体系中溶解性有机物分子量随着反应的进行而降低,腐殖化程度降低。利用GC-MS定性出渗滤液原液中47种有机物,该类有机物在Fenton反应后上清液中未再检出,但5种物质（邻苯二甲酸二（2-乙基己）酯、植酮、角鲨烯、麥角甾烷醇和二氢胆固醇）在沉淀的铁泥中检出。研究发现不同pH值、H2O2和Fe2+浓度条件下,残留的COD与DOM、TOC和UV254存在显著的相关关系（R2> 0.9）。本研究结果为改进垃圾渗滤液处理工艺和探索DOM在Fenton过程中的降解行为提供科学依据。     

典型南方水源溶解性有机物荧光特性变化与去除

于2014年4-9月,研究我国一典型南方水源溶解性有机物(DOM)的荧光特性变化与去除情况,同时分析了DOM荧光组分与三氯乙醛生成势(CHFP)的相关性。结果表明,该水源DOM主要以芳香性蛋白质类物质组成,溶解性微生物代谢产物类物质、富里酸类物质和腐殖酸类物质含量逐渐增加;5个荧光区域的积分体积(ΦⅠ,n、ΦⅡ,n、ΦⅢ,n、ΦⅣ,n和ΦⅤ,n)所占总体积(ΦT,n)平均比例依次为:13.55%、27.53%、25.00%、16.02%和17.91%;原水DOM的CHFP范围为27.06~81.20μg/L,平均值为46.60μg/L,三氯乙醛(CH)前体物含量与水体中溶解性微生物代谢产物类物质相关性最好;与常规处理工艺相比,O3/BAC深度处理工艺对于溶解性微生物代谢产物类物质的去除率大幅提高,更有利于CH的控制。     

基于三维荧光光谱-平行因子分析法的工业园区污水溶解性有机物溯源与归趋

本研究以某工业园区内的污水处理厂为研究对象,使用紫外-可见光谱和三维荧光光谱对11个进水管道和水处理各工艺段的水样进行检测,结合平行因子分析法探究了污水厂水体中主要污染物的来源和类别,最后对水质参数和各组分进行了相关性分析。紫外-可见光谱、三维荧光光谱结合平行因子分析结果表明,污水主要有5种荧光组分,其中C1,C2,C3均属于腐殖酸类物质;C4属于蛋白质类,近似于色氨酸类物质;C5属于新发现的组分。相关性分析结果表明, C3的荧光强度可以大致判断污水的芳香度, C2的荧光强度推断污水中的NH₃-N浓度,三维荧光光谱数据可以对水质参数评价进行补充。本研究可为发展高效低成本的污水厂尾水深度处理技术提供参考。     

南水北调中线清河溶解性有机物的光降解行为

溶解性有机物(dissolved organic matter, DOM)在水环境中普遍存在,其光降解行为与种类和来源密切相关。近年来,南水北调中线工程沿线中DOM含量过高问题逐渐引起了人们对饮用水水源水质的关注。利用三维荧光光谱与紫外可见吸收光谱表征了清河段DOM在水(Water DOM, W-DOM)、底泥(sediment-derived DOM, S-DOM)、藻胞内(intracellular DOM, I-DOM)和胞外(extracellular DOM, E-DOM)这4种典型来源中的光学性质和光降解行为。结果表明,W-DOM的主要来源是藻类代谢产生的E-DOM;S-DOM的主要形成原因是藻细胞破裂释放I-DOM。DOM的光漂白主要发生在紫外区,且UV-B波段的光漂白效率大于UV-A波段。W-DOM、S-DOM和E-DOM中有色DOM(chromophoric DOM, CDOM)的降解率基本相同,为40%~50%;I-DOM中CDOM降解率相对较低,约为25%。光照可以将W-DOM、S-DOM和E-DOM中复杂的大分子物质分解成结构简单的小分子物质。CDOM中类腐殖质的光降解率比类蛋白质更高,W-DOM、S-DOM和E-DOM中CDOM与类腐殖质的光降解速率在相同时间下基本保持一致;S-DOM和E-DOM中CDOM与类蛋白质的光降解速率在相同时间下基本保持一致。以上结果反映了太阳辐射对水环境中DOM的转化和去除机理,为河流水质保护提供了理论依据。     

Diagnosis of dissolved organic matter removal by GAC treatment in biologically treated papermill effluents using advanced organic characterisation techniques

Granular activated carbon (GAC) exhaustion rates on pulp and paper effluent from South East Australia were found to be a factor of three higher (3.62 cf. 1.47 kg m⁻³) on Kraft mills compared to mills using Thermomechanical pulping supplemented by Recycled Fibre (TMP/RCF). Biological waste treatment at both mills resulted in a final effluent COD of 240 mg L⁻¹. The dissolved organic carbon (DOC) was only 1.2 times higher in the Kraft effluent (70 vs. 58 mg L⁻¹), however, GAC treatment of Kraft and TMP/RCF effluent was largely different on the DOC persisted after biological treatment. The molecular mass (636 vs. 534 g mol⁻¹) and aromaticity (5.35 vs. 4.67 L mg⁻¹ m⁻¹) of humic substances (HS) were slightly higher in the Kraft effluent. The HS aromaticity was decreased by a factor of 1.0 L mg⁻¹ m⁻¹ in both Kraft and TMP/RCF effluent. The molecular mass of the Kraft effluent increased by 50 g mol⁻¹ while the molecular mass of the TMP/RCF effluent was essentially unchanged after GAC treatment; the DOC removal efficiency of the GAC on Kraft effluent was biased towards the low molecular weight humic compounds. The rapid adsorption of this fraction, coupled with the slightly higher aromaticity of the humic components resulted in early breakthrough on the Kraft effluent. Fluorescence excitation-emission matrix analysis of the each GAC treated effluent indicated that the refractory components were higher molecular weight humics on the Kraft effluent and protein-like compounds on the TMP/RCF effluent. Although the GAC exhaustion rates are too high for an effective DOC removal option for biologically treated pulp and paper mill effluents, the study indicates that advanced organic characterisation techniques can be used to diagnose GAC performance on complex effluents with comparable bulk DOC and COD loads.     

基于三维荧光及平行因子分析的南昌市某河可溶性有机物溯源及治理策略

地表河流污染物溯源对污染物防治及河流生态环境改善具有重要意义。三维荧光光谱(3D-EEM)的图谱形状、荧光峰位置、荧光峰强度、荧光峰个数信息和荧光参数可作为水体中可溶性有机物(DOM)的荧光特征。结合平行因子分析(PARAFAC)对南昌市某河的3D-EEMs进行分析并进行DOM溯源研究,结果表明,该河DOM主要包含3个荧光组分,分别为类腐殖质荧光组分C1(λ_Ex/λ_Em=245 nm/430 nm)、类氨基酸和类腐殖质组分的混合物C2(λ_Ex/λ_Em=240,300 nm/365 nm)和类色氨酸荧光组分C3(λ_Ex/λ_Em=225,275 nm/335 nm),分别占总荧光组分的35.93%,26.62%和37.45%。该河基本满足地表水环境质量标准(GB 3838-2002)III类水标准,浮游植物主要为蓝绿藻,河流中磷的来源复杂。污染物溯源结果表明,该河DOM腐殖化程度较低,生物活性较强,主要来源于浮游植物和微生物代谢降解和沉积物在冲击和水力作用下产生的内源污染。建议该河采用生态修复技术并辅助水体曝气系统治理DOM污染,并持续防止河流引入外源污染。     

先锋草本植物凋落物源溶解性有机质对典型汞铊矿废渣中重金属释放特征的影响

先锋草本植物广泛应用于尾矿堆场生态恢复,其凋落物分解是尾矿中溶解性有机质(DOM)的重要来源。然而,先锋草本植物凋落物源DOM对尾矿中重金属释放特征的影响尚不清晰。本研究以典型汞铊矿废渣及三叶草凋落物为研究对象,通过开展批次培养实验探讨了三叶草凋落物源DOM对废渣中重金属(Hg、As、Sb、Tl)释放特征的影响。结果表明,三叶草凋落物源DOM的成分主要为类络氨酸类物质、陆生类腐殖质物质和微生物类腐殖质物质。DOM的添加明显促进废渣中Hg和As的释放,抑制Tl和Sb的释放,浸出液中重金属的浓度依次为As>Tl>Hg>Sb。DOM的添加有利于废渣中Hg(Ⅱ)的溶出,促进废渣中As(Ⅴ)还原为As(Ⅲ)。主成分和相关性分析结果表明,DOM的自身组分及其对环境条件(pH、Eh)的改变是影响废渣重金属释放特征的主要因素。以上研究结果可为深入认识开展生态修复的废渣堆场上重金属的地球化学过程及环境风险提供参考。     

An overview of the methods used in the characterisation of natural organic matter (NOM) in relation to drinking water treatment

Natural organic matter (NOM) is found in all surface, ground and soil waters. During recent decades, reports worldwide show a continuing increase in the color and NOM of the surface water, which has an adverse affect on drinking water purification. For several practical and hygienic reasons, the presence of NOM is undesirable in drinking water. Various technologies have been proposed for NOM removal with varying degrees of success. The properties and amount of NOM, however, can significantly affect the process efficiency. In order to improve and optimise these processes, the characterisation and quantification of NOM at different purification and treatment processes stages is important. It is also important to be able to understand and predict the reactivity of NOM or its fractions in different steps of the treatment. Methods used in the characterisation of NOM include resin adsorption, size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) spectroscopy, and fluorescence spectroscopy. The amount of NOM in water has been predicted with parameters including UV-Vis, total organic carbon (TOC), and specific UV-absorbance (SUVA). Recently, methods by which NOM structures can be more precisely determined have been developed; pyrolysis gas chromatography-mass spectrometry (Py-GC-MS), multidimensional NMR techniques, and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The present review focuses on the methods used for characterisation and quantification of NOM in relation to drinking water treatment.     

Source Apportionment of Particulate Matter (PM10) and Indoor Dust in a University Building

A study on source apportionment of indoor dust and particulate matter (PM₁₀) composition was conducted in a university building by using chemometrics. The objective of this study was to investigate the potential sources of selected heavy metals and ionic species in PM₁₀ and indoor dust. PM₁₀ samples were collected using a low-volume sampler (LVS) and indoor dust was collected using a soft brush. Inductively coupled plasma spectrometry (ICP-MS) was used to determine the concentration of heavy metals, while the concentration of cations and anions was determined by atomic absorption spectrometer (AAS) and ion chromatography (IC), respectively. The concentration of PM₁₀ recorded in the building throughout the sampling period ranged from 20 ± 10 μgm^?3 to 80 ± 33 μgm^?3. The composition of heavy metals in PM₁₀ and indoor dust were dominated by zinc (Zn), followed by lead (Pb), copper (Cu), and cadmium (Cd). Principle component analysis (PCA) and multiple linear regression (MLR) showed that the main sources of pollutants in PM₁₀ came from indoor renovations (73.83%), vehicle emissions (16.38%), earth crust sources (9.68%), and other outdoor sources (0.11%). For indoor dust, the pollutant source was mainly earth crust. This study suggests that chemometrics can be used for forensic investigation to determine the possible sources of indoor contaminants within a public building.