三维荧光光谱区域积分法解析辽河七星湿地水体DOM组成及来源

监测了七星湿地水体水质,采用三维荧光光谱技术结合荧光区域积分(FRI)分析法研究七星湿地水体中溶解性有机物(DOM)荧光特性,分析了DOM组成、腐殖化程度、污染来源等与其他水质指标之间的相关性。结果表明,七星湿地对于支流水体有一定的净化作用,出水CODCr满足GB 3838—2002的Ⅴ类水质标准,氨氮及总磷仍然是水体中的主要污染物;荧光指数(f450/500)平均值为1.82,表明七星湿地DOM主要是生物来源;腐殖化指数(rB,D)整体较低,表明湿地水体腐殖化程度较高,有机物污染较为严重。通过荧光区域积分法将荧光光谱图划分为五大类,其中芳香性蛋白类物质Ⅱ相对浓度最高,占DOM总量的37.51%~54.2%,其主要与生活污水排放有关;DOC浓度与芳香蛋白类物质Ⅰ、芳香蛋白类物质Ⅱ、溶解性微生物代谢产物及腐殖质类物质有较高相关性;TP浓度则与芳香蛋白类物质Ⅱ呈显著正相关,与富里酸类物质和腐殖酸类物质显著相关。三维荧光光谱区域积分法可用于水体中DOM组成及污染物来源研究。     

褐水厌氧共消化中DOM荧光光谱特征及效应研究

文章以褐水(粪便)为底物,研究了不同共基质添加对厌氧消化甲烷产量的影响,并对过程中溶解性有机物(DOM)的三维荧光特征进行探究,研究了有机组分的变化对产甲烷的影响关系。结果表明,花生秸秆共消化组和褐水单消化组的累积甲烷产量分别为649和309 mL/g VS。采用三维荧光光谱结合平行因子分析发现,褐水单独消化和共消化过程的DOM均以微生物内源性产生为主。厌氧消化后,各反应器中色氨酸类蛋白荧光峰强度均显著降低,褐水单消化组的类腐殖质有所增加。4组条件消化全过程的DOM含有4个组分:紫外腐殖酸类、微生物源腐殖酸类、色氨酸类和酪氨酸类。褐水单消化组的类蛋白质组分(色氨酸、酪氨酸类)荧光强度综合较低,腐殖质类组分荧光强度相对较高,难以生物降解,这导致了厌氧效率不佳。共基质添加可以调节体系碳氮比和溶解性有机物含量,降低褐水厌氧消化中的类腐殖质的比例,并提高甲烷产率。     

餐饮废水MBR处理过程中DOM的三维荧光光谱分析

采用三维荧光(EEM)光谱技术,对膜-生物反应器(MBR)处理餐饮废水过程中的各种溶解性有机物(DOM)进行分析,并对比研究不同水质和容积负荷下DOM的EEM光谱的迁移变化特性和DOM中荧光物质对膜污染速率的影响.结果表明,各种DOM的荧光物质中,蛋白质类物质所占的比重最大,且溶解性微生物代谢产物(SMP)和附着型胞外聚合物(EPS)中的蛋白质类荧光物质对膜污染速率的影响最大,而紧密附着胞外聚合物(TB-EPS)中蛋白质类荧光物质强度与膜污染速率呈强烈的负相关性.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.     

污水厂二级出水中THMs前体物卤代活性荧光光谱分析

通过分析城市污水处理厂二级出水中溶解性有机物(DOM)及其XAD树脂分级组分的荧光光谱,研究了DOM的结构特性以及DOM中的THMs前体物在加氯消毒过程中的反应特性与荧光强度之间的相关性.三维荧光光谱显示DOM分级组分中均存在富里酸类、腐殖酸类、芳香性蛋白质类及微生物沥出物类荧光特征峰, 且以芳香性蛋白质类和富里酸类荧光物质为主.荧光光谱区域积分法(FRI)定量分析结果表明,4类荧光物质在DOM各分级组分中的累计荧光强度(ΦT,n)分布与其在二级出水中的分布趋势较相似,总体上呈现疏水性有机酸(HPO–A) >过渡亲水性有机酸 (TPI-A)>过渡性亲水性中性物质(TPI-N)>疏水性有机中性物质(HPO-N)>亲水性物质(HPI).此外,ΦT,n与单位浓度DOC在紫外254nm处的吸光度值(SUVA)及三氯甲烷生成活性(STHMFP)有较好的相关性,但与DOC相关性较差.同步荧光光谱结果表明,在单位DOC条件下,总DOM中稠环类芳香性物质的含量高于DOM各分级组分,而DOM各分级组分中稠环类芳香性物质的含量少于腐殖酸类物质的含量.     

气体分离循环对高温厌氧消化过程的影响

采用厌氧序批式反应器,研究了气体循环(包括气体直接循环和脱除气体中的氢气后循环)对以葡萄糖和乙酸钠配制的模拟废水在高温厌氧消化过程中乙酸代谢速率、出水性质及微生物相的影响,并采用尺寸排除色谱和三维荧光光谱技术,对溶解性微生物产物(SMP)的分子量分布和荧光物质组成进行了分析.结果显示,气体循环使得出水中残余挥发性脂肪酸的浓度由238.2mg/L(未脱氢)和129.6mg/L(脱氢)分别减少至8.5mg/L和8.2mg/L,并最终降低了SMP产量,45d时分别降至气体循环前的36.8%和59.2%.脱氢气体循环促进了乙酸化和乙酸氧化,导致了微生态环境和甲烷化基质浓度的差异,促进了高分子量SMP向低分子量SMP的转化,污泥中的微生物形态亦发生了较大变化.可见气体循环改善了基质与微生物的混合状况,改善了出水水质,而脱氢气体循环加速了乙酸的代谢,有望更快速地解除易降解有机物高温厌氧消化过程中的酸抑制,提高厌氧消化效率.     

A/O-MBR处理餐饮废水过程中DOM特性解析

借助凝胶过滤色谱(GFC)分子量测定技术和三维荧光(EEM)光谱技术,对厌氧微网与好氧平板膜-生物反应器(A/O-MBR)联合处理餐饮废水过程中各阶段的溶解性有机物(DOM)及污泥胞外聚合物(EPS)的性质进行研究。分子量研究表明:好氧段污泥滤液的GFC谱图中在10 min以前有大分子物质析出,分析是微生物代谢产物;且随着处理过程的进行水样DOM中的分子量分布范围不断变宽。EEM光谱研究表明:进水、好氧段出水、好氧段污泥滤液的DOM中的2种主要荧光物质为高激发波长类色氨酸和可见区类富里酸,而厌氧段出水中仅有高激发波长类色氨酸,且峰强较强。同时,厌氧段出水中在形成可见区类富里酸的区域内有成峰趋势,分析是由较强的类色氨酸峰的掩蔽作用造成的。好氧段污泥EPS中存在3个明显的荧光峰,指示了色氨酸和腐殖酸的存在。     

海拔梯度上川西高山土壤溶解性有机质(DOM)光谱特征

采用三维激发发射矩阵荧光光谱、平行因子分析（EEM-PARAFAC）和荧光区域积分方法（FRI）,研究川西高原3200~4000m高寒土壤DOM特征及其在海拔梯度上变化规律.结果表明,高寒土壤DOC含量为0.47~0.81g/kg,随着海拔梯度的升高而呈增加趋势,表层土中含量多高于亚表层土;土壤中DOM组分均呈5个组分,即芳香蛋白类物质I（酪氨酸类,Peak I）、芳香蛋白类物质II（BOD₅,Peak II）、富里酸类（Peak III）、微生物代谢产物（色氨酸类,Peak IV）和腐殖酸类（大分子腐殖酸,Peak V）;高山土壤DOM中以富里酸类有机质和腐殖酸类有机质组分为主,FRI值均随着海拔的升高而降低..川西高山土壤DOM荧光特征参数（荧光指数FI、自生源指数BIX、腐殖化指数HIX、新鲜度指数β：α）表明,土壤DOM的稳定性随着海拔升高而降低,生物有效性随着海拔升高而升高.因此,气候变暖可能将导致高海拔土壤DOM分解加剧而含量降低,但稳定性升高.     

ASBR处理食品废水中DOM转化过程的荧光光谱

利用厌氧序批式反应器(ASBR)处理食品废水,结合三维荧光光谱技术考察不同反应时段废水中溶解性有机物(DOM)的光谱特征和物质来源,并建立DOM特征峰荧光强度与氨氮浓度的关系.工艺运行结果表明:食品废水经过ASBR处理后,进水的COD从1100mg/L降至91mg/L,COD去除率达到91.73%,说明ASBR反应器可有效降解食品废水中的有机物质.三维荧光光谱显示,5种物质的特征荧光峰,即高激发波长色氨酸(峰A)、低激发波长色氨酸(峰B)、可见光区富里酸(峰C)、紫外光区富里酸(峰D)、类腐殖酸(峰E).随着厌氧生物处理的进行,峰A、峰B和峰C的荧光强度表现为先增加后减少的趋势;峰D荧光强度表现为微弱增加趋势;峰E荧光强度为先减少后增加趋势.荧光光谱指数FI、HIX、BIX表明,废水具有明显生物源特征.建立高激发波长色氨酸、低激发波长色氨酸特征峰荧光强度与色氨酸荧光强度之和与氨氮浓度在反应周期内的相关性,其相关系数分别为0.8136、0.9390、0.9153,说明可通过三维荧光光谱技术快速监测食品废水厌氧生物处理过程中的氨氮浓度.     

EGSB+A/O工艺处理玉米深加工废水出水中DOM特性分析

采用超滤膜法对某玉米深加工污水站EGSB+AO工艺二沉池出水进行分级,结合总溶解性有机碳(DOC)浓度、UV254和三维荧光光谱分析出水中溶解性有机物分子质量分布特性。结果表明,玉米深加工废水二级出水中溶解性有机物以分子质量大于10 k和小于0.5 k物质为主,这2个区间组分的芳香度较高。三维荧光谱图分析表明,出水主要含有色氨酸类蛋白和腐殖质,各分子质量区间的腐殖质荧光强度大于同分子质量的蛋白质类物质,而腐殖质是在好氧曝气阶段生成。各分子质量区间有机物的总荧光强度和DOC浓度、UV254呈显著线性相关。     

受四环素影响的活性污泥胞内外聚合物特征

利用离心加超声的方法对处理四环素抗生素废水的活性污泥胞外聚合物(EPS)和胞内聚合物(IPS)进行提取,将其分为-溶解型胞外聚合物(slime)、松散附着型胞外聚合物(LB)、紧密附着型胞外聚合物(TB)、胞内聚合物(IPS).用BCA法和蒽酮-硫酸法测定了各层EPS和IPS溶液中的蛋白质和多糖含量,同时用三维荧光光谱扫描(EEM)和同步荧光光谱扫描(SFS)对其中的溶解性有机物(DOM)进行定性和定量分析,结果表明在EPS中的蛋白质和多糖的含量高于IPS,且蛋白质含量均比多糖含量高,而在slime和IPS中的蛋白质和多糖的含量高于LB和TB;低激发波长类色氨酸和高激发波长类色氨酸是EPS和IPS溶液的主要成分,且溶液中的溶解性代谢产物和芳香蛋白类物质相对含量在slime、LB、TB和IPS逐渐增加,而难降解有机物-腐殖酸类物质的相对含量逐渐降低;进水四环素浓度与污泥各层EPS和IPS溶液中DOM也具有较好的相关性;三维荧光法检测溶液中的DOM与化学分析测试出的蛋白质含量具有较好的相关性.     

pH值对SBR生物反应器出水溶解态有机质含量与构成的影响

为探讨污水二级生化出水中有机物(EfOM)的构成特点和变化规律,采用配置生活污水,对不同pH值运行条件下, SBR生物反应器出水中的溶解态有机质(DOM)含量和构成进行了比较研究.结果表明,运行期间pH值的调节对SBR反应器出水DOM含量与构成的影响均较大.初始pH为6.5的SBR反应器, pH值降低为6.0后,出水DOC由原来的4.0mg·L-1不断升高,进一步提高pH值,能够起到一定的缓解作用;初始pH为8.0的SBR反应器,出水DOC从4.0mg·L-1快速降低并保持在2mg·L-1左右, pH值降低为6.5后, DOC变化不大.单宁酸和蛋白质、碳水化合物、DNA等微生物代谢产物(SMPs)是出水DOM的主要组成部分, pH值对SMPs生成的影响是一个长期的过程,运行过程中降低pH值,造成出水SMPs含量不断升高. pH值对整个循环过程中溶解态有机物降解情况的影响,在厌氧阶段发挥了主要作用,较高pH值有利于厌氧阶段有机物的降解,而好氧阶段的有机物降解受pH值影响不大.     

Molecular behavior and interactions with microbes during anaerobic degradation of bio-derived DOM in waste leachate

It is the key to control bio-derived dissolved organic matters (DOM) in order to reduce the effluent concentration of wastewater treatment, especially for waste leachate with high organic contaminants. In the present study, the anaerobic degradation of aerobically stabilized DOM was investigated with DOM substrate isolated through electrodialysis. The degradation of bio-derived DOM was confirmed by reduction of 15% of total organic carbon in 100 days. We characterized the molecular behavior of bio-derived DOM by coupling molecular and biological information analysis. Venn based Sankey diagram of mass features showed the transformation of bio-derived DOM mass features. Occurrence frequency analysis divided mass features into six categories so as to distinguish the fates of intermediate metabolites and persistent compounds. Reactivity continuum model and machine learning technologies realized the semi-quantitative determination on the kinetics of DOM mass features in the form of pseudo-first order, and confirmed the reduction of inert mass features. Furthermore, network analysis statistically establish relationship between DOM mass features and microbes to identify the active microbes that are able to utilize bio-derived DOM. This work confirmed the biological technology is still effective in controlling recalcitrant bio-derived DOM during wastewater treatment.     

Removal of anaerobic soluble microbial products in a biological activated carbon reactor

The soluble microbial products (SMP) in the biological treatment effluent are generally of great amount and are poorly biodegradable. Focusing on the biodegradation of anaerobic SMP, the biological activated carbon (BAC) was introduced into the anaerobic system. The experiments were conducted in two identical lab-scale up-flow anaerobic sludge blanket (UASB) reactors. The high strength organics were degraded in the first UASB reactor (UASB1) and the second UASB (UASB2, i.e., BAC) functioned as a polishing step to remove SMP produced in UASB1. The results showed that 90% of the SMP could be removed before granular activated carbon was saturated. After the saturation, the SMP removal decreased to 60% on the average. Analysis of granular activated carbon adsorption revealed that the main role of SMP removal in BAC reactor was biodegradation. A strain of SMP-degrading bacteria, which was found highly similar to Klebsiella sp., was isolated, enriched and inoculated back to the BAC reactor. When the influent chemical oxygen demand (COD) was 10,000 mg/L and the organic loading rate achieved 10 kg COD/(m 3 ·day), the effluent from the BAC reactor could meet the discharge standard without further treatment. Anaerobic BAC reactor inoculated with the isolated Klebsiella was proved to be an effective, cheap and easy technical treatment approach for the removal of SMP in the treatment of easily-degradable wastewater with COD lower than 10,000 mg/L.     

渗滤液与城市污水合并处理过程的有机物去除特征

以上海老港垃圾填埋场调蓄池的渗滤液,及其经厌氧甲烷化垃圾填埋柱循环回灌处理后的出水和其再经过混凝处理后的出水等3种不同处理水平的渗滤液为研究对象,分别以不同的比例与城市污水混合,采用好氧活性污泥法合并进行处理,对进出水的COD、UV254吸光度和溶解性有机物的分子量分布及污泥的脱氢酶活性进行了测定分析．结果表明：当渗滤液混合比例小于10％时,出水的COD和UV254吸光度随混合比例线性升高,污泥的活性相应线性降低;而当混合比例大于20％时．污泥活性阶跃降低,出水COD和UV254吸光度的升高超出线性范围．渗滤液混合比例为20％与比例为5％的混合污水相比．分子量1k～4k的溶解性有机物去除率显降低．渗滤液与城市污水合并处理的混合比例大于10％时,微生物的有机物降解能力会受到严重损害,且常规的渗滤液生物和物化预处理不能减轻此种损害．     

Evaluation of factors influencing soluble microbial product in submerged MBR through hybrid ASM model

In this study, a mathematical model was established to predict the formation of the soluble microbial product (SMP) in a submerged membrane bioreactor. The developed model was calibrated under the reference condition. Simulation results were in good agreement with the measured results under the reference condition. The calibrated model was then used in the scenario studies to evaluate the effect of three chosen operating parameters: hydraulic retention time (HRT), dissolved oxygen concentration, and sludge retention time (SRT). Simulation results revealed that the SMP dominated the soluble organic substances in the supernatant. The scenario studies also revealed that the HRT can be decreased to 1 h without deteriorating the effluent quality; dissolved oxygen concentration in the reactor can be kept at 2–3 mg/L to maintain the effluent quality, reduce the content of SMP, and minimize operating costs; the optimal SRT can be controlled to 10–15 d to achieve complete nitrification process, less membrane fouling potential, and acceptable organic removal efficiency.     

基于EEM-PARAFAC解析厌氧生物滤池对城市污染河流中DOM的转化特性

为探究厌氧生物滤池(AF)处理城市污染河流的最佳工况和运行效能,以新河河水为研究对象,运用三维荧光光谱结合平行因子法(EEM-PARAFAC),研究AF中试试验系统在不同水力停留时间(HRT)及温度条件下对溶解性有机物(DOM)的转化特性. 结果表明:①河水中DOM主要包含3种荧光组分,其中,C1为类腐殖质物质,C2为类蛋白物质,C3为类腐殖质物质,类蛋白和类腐殖质物质平均占比分别为53.45%和46.55%. ②AF运行稳定后COD平均去除率为30.75%,出水UV₂₅₄降低19.80%;荧光组分分析表明,DOM的降低主要归因于C2和C3的有效转化,且提高温度和HRT有助于DOM的进一步降低. ③UV₂₅₄和<10 kDa的DOM沿程逐步减小,3~10 kDa和<3 kDa的DOM去除率分别为64.29%和22.81%;沿程出水三维荧光光谱显示,AF前端微生物活性较高,C1和C3变化较小,C2先升高后逐步下降,最终出水DOM总荧光强度出现明显的降低,表明AF第1级滤层是DOM去除和转化的主要区域. 研究显示,常温且HRT=24 h工况下,AF能够在一定程度上将难降解有机物转化为易降解有机物,有效去除城市污染河流中的DOM,可作为处理城市污染河流的潜在预处理手段.      

Relationship between heavy metals and dissolved organic matter released from sediment by bioturbation/bioirrigation

Organic matter (OM) is an important component of sediment. Bioturbation/bioirrigation can remobilize OM and heavy metals that were previously buried in the sediment. The remobilization of buried organic matter, thallium (Tl), cadmium (Cd), copper (Cu) and zinc (Zn) from sediment was studied in a laboratory experiment with three organisms: tubificid, chironomid larvae and loach. Results showed that bioturbation/bioirrigation promoted the release of dissolved organic matter (DOM) and dissolved Tl, Cd, Cu and Zn, but only dissolved Zn concentrations decreased with exposure time in overlying water. The presence of organisms altered the compositions of DOM released from sediment, considerably increasing the percentage of fulvic acid-like materials (FA) and humic acid-like materials (HA). In addition, bioturbation/bioirrigation accelerated the growth and reproduction of bacteria to enhance the proportion of soluble microbial byproduct-like materials (SMP). The DOM was divided into five regions in the three-dimensional excitation emission matrix (3D-EEM), and each part had different correlation with the dissolved heavy metal concentrations. Dissolved Cu had the best correlation with each of the DOM compositions, indicating that Cu in the sediment was in the organic-bound form. Furthermore, the organism type and heavy metal characteristics both played a role in influencing the remobilization of heavy metal.     

自然光和UV辐照下二级出水DOM及毒性的变化

为了探明自然光和紫外光(UV)对二级处理出水中溶解性有机物(DOM)及其毒性效应的削减特性,研究了在自然光和UV两种不同光源的辐照条件下,二级处理出水中DOM的光谱特性、遗传毒性和植物毒性变化,阐明了毒性效应变化的成因.结果表明:相比于自然光照,UV辐照可以明显降低二级处理出水的UV254,并达到21％矿化.自然光和U...