京密引水中天然有机物的形态

用改进的Ｌｅｅｎｈｅｅｒ分离方法，并引入最新的ＸＡＤ－８，ＸＡＤ－４树脂串联技术，将京密引水中有机物定量分离为悬浮和溶解态两大类。后者又进一步分离为憎水有机物、腐殖酸类，ＸＡＤ－４酸和亲水中性有机物等形成。溶解态有机物含量约为３ｍｇＣ／ｌ，其中一半左右为腐殖酸类。ＸＡＤ－４酸占溶解态有机１５－２０％，非极性憎水有机物所占比例很低。     

污水厂尾水及受纳河流样品溶解有机物(DOM)的分子光谱解析及识别

为了研究污水厂尾水对受纳水体的影响,采用XAD-8和阴阳离子交换树脂联用技术,对合肥市污水厂不同处理工艺出水以及朱砖井污水厂受纳河流上下游水样进行分离富集处理,获得了亲水性碱(HIB)、亲水性酸(HIA)、亲水性中性物质(HIN)、憎水性碱(HOB)、憎水性酸(HOA)和憎水性中性物质(HON) 6种组分。采用DOMfluor、PARAFAC、PAC投影等数学分析方法,将前述5种树脂分离组分以及原水水样的荧光光谱进行解析,获得类蛋白质、类富里酸和类胡敏酸3种主成分。结合溶解有机碳分析结果,得到DOM总有机物中憎水性有机质约占75%,主要为类富里酸和类胡敏酸等憎水性腐殖质。结合傅里叶变换红外光谱分析结果,发现亲水性物质主要包含多糖、蛋白质和磷酸盐化合物等物质,憎水性物质HOA、HOB主要包含脂类和有机酸等。通过比较二十埠河上下游水样以及树脂分离后组分的主成分得分值,发现纳污河流污染较重,污水厂尾水对受纳水体水质影响较小。     

电化学氧化垃圾渗滤液生化出水过程中溶解性有机物形态及可生化性

以垃圾渗滤液生化出水为研究对象,利用Ti/RuO_2阳极和Cu-Zn阴极进行电化学氧化去除溶解性有机物机理研究.应用三维荧光光谱对垃圾渗滤液生化出水溶解性有机物组成、结构变化和官能团变化进行分析,并对反应过程中垃圾渗滤液生化出水可生化性变化进行研究.结果表明,垃圾渗滤液生化出水中溶解性有机物主要由类富里酸类物质、类胡敏酸类物质和可溶性微生物降解产物为主,类色氨酸类物质和类酪氨酸类物质含量较低;反应过程中溶解性有机物的腐殖化程度降低,芳香性减弱,苯环上连接的极性基团率先被氧化去除;Ti/RuO_2-Cu/Zn电化学氧化体系降解垃圾渗滤液生化出水有机物,主要依赖生成次氯酸的间接氧化作用.电化学氧化过程中垃圾渗滤液生化出水可生化性增强.     

二级出水中溶解性有机物的分级表征特性

以城市污水厂二级出水为研究对象,利用大孔吸附树脂将污水中溶解性有机物(Dissolved organic matter,DOM)分离成疏水酸性、中性、碱性物质和亲水性物质等4个组分,同时分析了各组分的有机物特性.结果表明,二级出水溶解性有机物中疏水酸性物质是二级出水溶解性有机物的主要组成部分.4种组分中均含有腐殖质类物质,疏水酸性物质(Hydrophobic acids,HOA)和疏水中性物质(Hydrophobic neutrals,HON)中腐殖酸类峰的荧光强度较大,亲水性物质(Hydrophilic fraction,HI)中的蛋白峰荧光强度较大.腐殖质类物质分子量分布较为单一,主要分布在0.9 k Da左右,而疏水性组分蛋白类物质分子量分布较为广泛,在200 k Da左右及小于9 k Da时均有一定分布,亲水性组分蛋白类物质主要由分子量小于9 k Da的物质组成.X射线光电子能谱(X-ray photoelectron spectroscopy,XPS)分析结果表明,HOA、HON中含有较多的芳香族化合物,而疏水碱性物质(Hydrophobic bases,HOB)、HI中则含有较多的羰基和羧基类官能团.     

沉积物间隙水溶解态磷和铁（Ⅱ）高分辨同步分析方法的研究

沉积物具有高度的空间异质性,尤其在沉积物-水界面附近的微环境中,溶质在微小尺度上可能存在强烈的浓度梯度分布,需要借助高分辨的获取技术才能表征。本研究发展了一种沉积物微界面溶解态反应性磷（Dissolved Reactive Phosphorus,DRP）和溶解态铁（Ⅱ）的同步分析方法。利用分辨率为4 mm、平衡时间仅为2 d的微型间隙水平衡装置（Peeper装置）获取微量间隙水（～100μL·样品-1）,采用384微孔板微量比色法分别测定同一间隙水样品中的DRP和溶解态铁（Ⅱ）的质量浓度,单一指标所消耗的间隙水体积由5 mL减少到仅～40μL,检出限分别为0.009和0.017 mg·L-1,精密度为1%～7%,均与常规方法相近。将该分析方法应用到太湖两个湖区的沉积物中,同步获得的微界面溶解态磷和铁（Ⅱ）的分布较好地反映了两者的关系。     

黄浦江原水中各类有机物在铝盐混凝过程中的去除效果

通过XAD-8/XAD-4吸附树脂联用技术将黄浦江微污染原水中溶解性有机物分为疏水酸、非酸疏水物质、弱疏水物质及亲水物质4类有机物,研究了铝盐混凝工艺对黄浦江水中4类有机物的去除效果.硫酸铝在最佳混凝条件下,即投加量为8 mg·l~(-1)(以Al计),pH=5.5时,水中的DOC和UV_(254)的去除率分别达到23%和32%.有机物的亲疏水性对混凝工艺有较大影响,混凝法倾向于优先去除水中疏水性有机物,而疏水性有机物的酸碱性对混凝工艺没有明显影响,酸性和非酸类疏水物质均能破混凝工艺所去除.疏水酸是水中最主要的三氯甲烷类消毒副产物的前体物质,混凝工艺对于三氯甲烷类消毒副产物有良好的控制作用,总体减少了 39%的生成量.而不同类的有机物之间,混凝工艺对消毒副产物控制效果不同,其中对疏水酸的控制三氯甲烷消毒副产物的效果最好,减少了63%的生成量,亲水物质的控制效果最差,三氯甲烷生成量仪减少了3%.疏水酸表现出比亲水物质更强的生物毒性,混凝工艺能明显降低原水的毒性.     

富营养化湖泊藻型及草型区微生物群落对有色可溶有机物组成的影响

有色可溶有机物(CDOM)是水生生态系统溶解有机碳储库的主要组成,在湖泊生态系统结构、初级生产力以及物质交换等方面发挥着重要作用。研究秋季太湖藻型区—蓝藻死亡时期及草型区—水草腐烂时期CDOM的组成差异性特征及其影响因素。首先对两类典型湖区水体的理化性质进行了分析,然后利用紫外可见光谱、三维荧光光谱结合平行因子分析的技术确定CDOM组成,最后结合Illuminar高通量测序揭示了两个区域水体中不同的微生物群落结构对CDOM组成的影响。结果表明,藻型湖水的各理化性质指标,包括NH4~+-N、NO2~--N、NO3~--N、TN,TP,DOC的浓度都明显高于草型湖水,秋季藻源性CDOM的含量明显高于草源性CDOM的含量。虽然藻源性和草源性CDOM的荧光组分相同,即同为类腐殖、类色氨酸和类络氨酸荧光组分,然而,相比于草源性CDOM,荧光指数(FI)和腐殖化指数(HIX)均表明藻源性CDOM具有更高的分子量组成,更难被微生物利用,而造成此差异性的重要原因为两个区域微生物群落组成的差异性,藻型区水体含有更丰富的降解有机物的细菌种类,包括黄杆菌属(Flavobacterium),噬氢菌属(Hydrogenophaga)、生丝微菌属(Hyphomicrobium)等,可优先分解易于分解的有机物,残留更多难降解的有机物,具有更大的潜在的环境隐患。     

中国三个不同富营养化湖泊沉积物中Cu、Zn赋存特征及其与营养盐的相关性分析

对太湖、南四湖、白洋淀三个不同富营养化湖泊沉积物进行采样,采用Tessier连续提取法,测定了3个湖泊表层沉积物中Cu、Zn两种重金属的赋存形态,并初步探讨了重金属各形态与沉积物及上覆水中营养盐的相关关系。结果表明,沉积物中重金属总量以白洋淀最高,太湖最低,但重金属污染程度为太湖＆gt;南四湖＆gt;白洋淀,太湖Cu污染指数为1.34~1.6,白洋淀Cu污染指数仅为0.79~1.17。沉积物中重金属赋存形态Cu主要以残渣态和有机质结合态为主（二者之和占73%以上）, Zn则以残渣态和Fe-Mn氧化态占优（二者之和比例达83%以上）,含量最少的均为可交换态。不同湖泊沉积物重金属赋存形态差异较大,太湖残渣态重金属占总量的比例最小（Cu为43%~56%,Zn为49%~63%）,南四湖残渣态占的比例最大（Cu为59%~82%、Zn为64%~77%）;可交换态比重在太湖中最高（Cu占3.2%~5.6%,Zn为1.3%~1.5%）,在南四湖中最低（Cu为1.1%~2.9%,Zn未检出）。从“非稳定态”重金属（除残渣态外的四种形态之和）所占比例看,相较其它两个湖泊,太湖沉积物中重金属污染人为输入的活性态占较大比重,具有较高的二次释放风险。相关性分析得出,重金属Cu的可交换态与上覆水中总氮及总磷之间存在着极显著的正相关关系,碳酸盐结合态Cu与沉积物中营养盐呈现出显著的负相关性,说明水体的富营养化程度加剧可能会增强沉积物中Cu向水体释放的风险。     

基于粒径分布的城镇污水有机组分赋存特征调查

本文以京津地区城镇污水为研究对象,利用滤膜法从粒径分布角度分析了城镇污水中总有机物与蛋白质、糖类、脂类及挥发性有机酸等有机组分的浓度水平,进而利用统计学手段解析其赋存特征.结果表明,蛋白类有机组分所占比例最高(46.9%—48.3%),而糖类(4.7%—11.0%)和脂类(3.4%—11.8%)含量相对较低,并且蛋白质类在不同粒径范围内均为占优组分.另外,调查区域的污水样品中富含颗粒态(100μm)及超胶体态(100—1μm)有机物,而胶体态(1—0.15μm)有机质含量最低;Spearman相关分析亦指出颗粒态和溶解态(0.001μm)有机物在污水中存在类似的环境归趋.从本研究结果来看,该区域污水处理厂可在保障水质达标的前提下,采取有效的固液分离及碳质转化手段,提高大粒径态有机物的资源化利用率.     

几种原料生物炭溶解性有机质(DOM)的光谱特征研究

溶解性有机质(DOM)在全球碳循环及污染物的迁移转化过程中起着重要作用,而光谱特征能快速识别DOM的主要来源和重要特征。研究针对几种原料(苹果枝、橘子枝、花生壳、水稻秸秆、玉米秸秆)在同一热解温度下制备的生物炭,采用紫外-可见吸收光谱、三维荧光光谱和傅里叶变换红外光谱相结合的方法对其释放的DOM光谱特征进行了研究。结果表明：秸秆类生物炭的溶解性有机碳(DOC)含量显著高于其他3种生物炭;紫外-可见光谱分析表明,5种生物炭DOM的芳香性组分含量均较少,腐殖化程度较低,亲水性组分占主导;三维荧光光谱分析表明,秸秆类生物炭DOM的荧光组分物质含量高于木质类和壳类,且各荧光组分含量占比中可溶性微生物降解产物和类胡敏酸比例最高;傅里叶变化红外光谱表明,5种生物炭DOM光谱特征相似,含有丰富的有机官能团(如羧基、酚羟基等)或半醌自由基等。     

焦化废水中溶解性有机物组分的特征分析

焦化废水是典型的具有复杂有机质的工业废水,其复杂的有机构成制约了水处理的水质达标,且可能对排入水体构成危害.为了探明其溶解性有机物的组成,采用XAD-8大孔树脂将焦化废水中的溶解性有机物分为亲水性组分(HIS)、疏水酸性组分(HOA)、疏水碱性组分(HOB)和疏水中性组分(HON),分析了各组分的溶解性有机物(DOC)、紫外-可见光谱、色度,并采用GC/MS对各组分中有机物进行定性分析.结果表明,焦化废水中的有机物主要为HIS和HOA组分,其DOC含量分别占总DOC的44.3%和32.4%;焦化废水在200—250 nm和300—400 nm范围内有特征吸收峰,且吸收光强度顺序为HIS>HOA>HON>HOB;焦化废水的色度主要由HOA和HON构成,其在525 nm和436 nm处的吸光度分别占焦化废水吸光度的42.9%(HON)、42.1%(HON)和21.4%(HOA)、15.8%(HOA);焦化废水中亲水性物质主要是苯胺、苯酚、喹啉、异喹啉,疏水酸性物质中主要是各种甲基取代的酚类物质,疏水碱性物质主要是各种胺类和含氮杂环化合物,疏水中性物质主要是吲哚及其衍生物.     

Scanning Electron Microscopy of Humic Substances Produced During Cellulose Decomposition

Humic substances (HS) produced during the aerobic decomposition of polysaccharides still need to be recognized as such and characterized. Humic (HA) and fulvic (FA) acids extracted at different time intervals during composting of cotton residues from carding, where no decomposition of lignin occurred, were investigated by scanning electron microscopy (SEM) size exclusion chromatography and infrared spectroscopy. Throughout the experiment, fulvic acids possessed a larger number of carboxyl groups but a lower number of weak acidic groups (negatively charged acid groups at pH 11) than humic acids. the number of carboxyl groups increased with time in both fulvic and humic acids, while that of phenolic groups decreased. Infrared spectra showed that the ratio between carboxyl and methyl groups decreased from 8.5 to 4 in FA after 18 days. This change corresponded with the disappearance of flat sheet structures observed by SEM at pH 6. Our results suggest that the shape of humic molecules as observed by SEM reflects the strength of hydrophilic/hydrophobic interactions with the solvent molecules. About 80% of FA molecules had a molecular weight lower than 3500 as deduced from column calibration with HS standards obtained by ultrafiltration. About 40% of humic acids were composed of small molecules; only 20% HA had a molecular weight larger than 45000. Polysaccharide-derived HS may not be limited to the high molecular weight poorly transformed fraction containing bonded polysaccharide structures, but may also consist of low molecular weight components with no structural similarity to the original material.     

Characterization of dissolved organic matter from saline soils by fluorescence spectroscopy

In this paper hydrophilic (HI) and hydrophobic (HO) fractions of dissolved organic matter (DOM) extracted from soils at different degrees of salinisation were characterised by means of fluorescence spectroscopy in the emission, excitation and synchronous-scan modes. Results provided evidence of the different chemical nature of DOM fractions and allowed to distinguish hydrophilic and hydrophobic fractions extracted from the same soil substrate. The strong decrease in fluorescence intensity observed with the increasing salinity of the soils can be utilised to obtain information on the salinity level of different soil substrates by comparison of spectral fluorescence intensities.     

Characterization of fulvic acids during olive mill waste composting (Elemental,Thermal and fluorescence analyses)

Elemental analysis, fluorescence spectroscopy and differential scanning calorimetry (DSC) were applied to the study of fulvic acids isolated from different stages during olive mill waste composting. The fulvic extracted acids are characterized by a high nitrogen content and O/C ratio values that may result from the high degree of humification and the synthesis of more condensed humic complexes. This was confirmed by fluorescence spectroscopy in the synchronous-scan mode by the decrease of shoulder intensities at intermediate wavelengths indicating the increase of polycondensation and conjugation of unsaturated structures and the greater uniformity of fluorophores. Fluorescence spectra in the emission, excitation and synchronous modes became simpler with compost maturation. This was confirmed by DSC results which proved the high degree of polycondensation of aromatic nuclei of fulvic acid molecules during olive mill waste composting.     

Characterization of fulvic acids during olive mill waste composting (Elemental, Thermal and fluorescence analyses)

Elemental analysis, fluorescence spectroscopy and differential scanning calorimetry (DSC) were applied to the study of fulvic acids isolated from different stages during olive mill waste composting. The fulvic extracted acids are characterized by a high nitrogen content and O/C ratio values that may result from the high degree of humification and the synthesis of more condensed humic complexes. This was confirmed by fluorescence spectroscopy in the synchronous-scan mode by the decrease of shoulder intensities at intermediate wavelengths indicating the increase of polycondensation and conjugation of unsaturated structures and the greater uniformity of fluorophores. Fluorescence spectra in the emission, excitation and synchronous modes became simpler with compost maturation. This was confirmed by DSC results which proved the high degree of polycondensation of aromatic nuclei of fulvic acid molecules during olive mill waste composting.     

Unwanted metals and hydrophobic contaminants in bioreactor effluents are associated with the presence of humic substances

Biological treatment of landfill leachate is challenging due to the presence of complex compounds. Here, we treated an old landfill leachate using a membrane bioreactor under the following conditions: 24 h for hydraulic retention, 65 days of sludge retention and an average organic load rate of 1.71 ± 0.16 g/L/day. We observed a high removal of ammonia, phosphorous and some metals. However, removal of organic carbon was incomplete. Despite a major removal of suspended solids, hydrophobic and volatile hydrophilic compounds, high concentration of fulvic acid and hydrophilic contaminants was found in the effluent. Overally, we demonstrate that the presence of humic substances in the effluent is associated with the detection of arsenic, copper and chromium and di(2-ethylhexyl) phthalate.     

Hepatoprotective activity of 1-(4-(Dimethylamino)Benzylidene)-5-(2-Oxoindolin-3-ylidene) Thiocarbohydrazone in rats

The aim of the present study was to evaluate the hepatoprotective activity of 1-(4-(dimethylamino)benzylidene)-5-(2-oxoindolin-3-ylidene) thiocarbohydrazone, a novel isatin derivative against carbon tetrachloride (CCl₄)-induced hepatotoxicity in rats. Hepatic damage was induced by administration of CCl₄ (1 ml/kg, b.w., p.o.) in combination with liquid paraffin (1:1) as a single dose. The hepatotoxic rats were treated with test compound at doses of 50 or 100 mg/kg for three days and liver damage biomarkers, including activities of serum glutamate pyruvate transaminase (SGPT), serum glutamate oxaloacetate transaminase (SGOT), serum alkaline phosphatase (ALP), and levels of total serum bilirubin (TB) measured in blood samples. Results demonstrated that treatment with test compound at doses of 50 or 100 mg/kg to hepatotoxic rats produced a significant dose-dependent reduction of elevated SGOT, SGPT, ALP activities and TB levels indicating a hepatoprotective effect that was confirmed by histopathological examination of liver tissues. The study results confirmed the hepatoprotective activity of 1-(4-(dimethylamino)benzylidene)-5-(2-oxoindolin-3-ylidene) thiocarbohydrazone in rats.     

Fluorescence spectroscopic studies of the effect of granular activated carbon adsorption on structural properties of dissolved organic matter fractions

This work investigated the effect of granular activated carbon adsorption (GACA) on fluorescence characteristics of dissolved organic matter (DOM) in secondary effluent, by means of excitation–emission matrix (EEM) spectra, the fluorescence regional integration (FRI) method, synchronous spectra, the fluorescence index defined as the ratio of fluorescence emission intensity at wavelength 450 nm to that at 500 nm at excitation (λ_ex)=370 nm, and the wavelength that corresponds to the position of the normalized emission band at its half intensity (λ_0.5). DOM in the secondary effluent from the North Wastewater Treatment Plant (Shenyang, China) was fractionated using XAD resins into 5 fractions: hydrophobic acid (HPO–A), hydrophobic neutral (HPO–N), transphilic acid (TPI–A), transphilic neutral (TPI–N) and hydrophilic fraction (HPI). Results showed that fluorescent materials in HPO–N and TPI–N were less readily removed than those in the other fractions by GACA. The relative content of fluorescent materials in HPO–A, TPI–A and HPI decreased whereas that in HPO–N and TPI–N increased as a consequence of GACA. Polycyclic aromatics in all DOM fractions were preferentially absorbed by GACA, in comparison with bulk DOM expressed as DOC. On the other hand, the adsorption of aromatic amino acids and humic acid-like fluorophores exhibiting fluorescence peaks in synchronous spectra by GACA seemed to be dependent on the acid/neutral properties of DOM fractions. All five fractions had decreased fluorescence indices as a result of GACA. GACA led to a decreased λ_0.5 value for HPO–A, increased λ_0.5 values for HPO–N, TPI–A and HPI, and a consistent λ_0.5 value for TPI–N.     

Chemical identification and genotoxicity analysis of petrochemical industrial wastewater

The actual harmful effects of industrial wastewater can not be reflected by the conventional water quality index. Therefore, the change in dissolved organic matter and the genetic toxicity of petrochemical wastewater were observed in the current study by examining the wastewater treatment plant of a large petrochemical enterprise in Northwest China. Using XAD-8, MSC, and DA-7 resins, the wastewater was separated into six fractions, namely, hydrophobic acid (HOA), hydrophobic neutral (HOB), hydrophobic alkaline, hydrophilic acid, hydrophilic alkaline, and hydrophilic neutral. Umu-test was used to detect the genetic toxicity of the wastewater samples, and fluorescence spectra were also obtained to examine genetic toxic substances. The results show that wastewater treatment facilities can effectively reduce the concentration of organic matter in petrochemical wastewater (p<0.05). However, the mixing of aniline wastewater can increase the amount of organic carbon (p<0.05) and can overload facilities. This finding shows that the mixed collection and joint treatment of different types of petrochemical wastewater can affect the water quality of the effluent. Particularly, hydrophobic substances can be difficult to remove and account for a relatively large proportion of the effluent. The mixture of aniline wastewater can increase the genetic toxicity of the effluent (p<0.05), and biologic treatment can not effectively decrease the toxicity. Most of the genetic toxicology may exist in the HOA and HOB fractions. Fluorescence spectroscopy also confirms this result, and tryptophan-like substances may play an important role in genetic toxicity.