巴松措表层沉积物中腐殖酸与富里酸的特性

采用紫外吸收光谱和GC-MS扫描解析,对西藏东南部湖泊巴松措表层沉积物中的腐殖酸和富里酸特性进行研究.结果表明,巴松措表层沉积物中腐殖酸和富里酸的紫外吸光度在200~400nm间较400~800nm间明显增加,富里酸在270nm附近出现弱而钝的双肩吸收,表明其中存在芳香环结构.腐殖酸和富里酸在254nm处的吸光度普遍偏低,表明其中难降解有机物的含量较低.通过紫外吸收特征值（A₄₆₅/A₆₆₅）分析得出,巴松措表层沉积物腐殖酸和富里酸的腐殖化程度较低.在人类活动频繁的区域,腐殖酸和富里酸的腐殖化程度相对于其他区域较高.根据GC-MS扫描解析,匹配度较高物质的分子式为C₁₅H₂₄,分子量为204,其结构中都含有芳香环,且含有脂肪链、不饱和烃、甲基、亚甲基、异丙基、环丙烷、己烷和萘等结构,均属于芳香族化合物,与紫外吸收光谱的分析结果一致.匹配度较高的物质推断属于类色氨酸.     

堆肥腐熟前后胡敏酸与富里酸的还原容量比较

采集腐熟前后的堆肥样品并提取和纯化出腐殖质(胡敏酸:HA;富里酸:FA),分别以柠檬酸铁(FeCit)和Fe(NO3)3作电子受体,测定了HA和FA的还原容量(RC).结果表明:以FeCit作为电子受体时,与未腐熟堆肥样品相比,腐熟后筛分样品HA的RC值增大,从22.85mmol e-/molC增大到26.84mmol e-/molC,而其对应FA的RC值减少,由37.67mmol e-/molC降低为33.68mmol e-/molC;对于两种不同形态的电子受体,以 FeCit为电子受体测定得到的RC值高于以Fe(NO3)3为电子受体测定得到的RC值;相对于本底还原容量,HA和FA经微生物还原后其RC值降低,降低幅度与微生物种类有关.结合紫外-可见光谱和三维荧光光谱分析发现,堆肥HA和FA的还原能力与其中类富里酸物质含量和醌基浓度成正相关,而与其本身的芳化度和分子量呈负相关.     

腐殖酸对高锰酸钾氧化苯酚的影响及其作用机制

以黄腐酸和黑腐酸为代表,研究了腐殖酸对高锰酸钾氧化苯酚的影响;采用Stevenson腐殖酸为模型,探讨了腐殖酸中不同官能团对高锰酸钾氧化苯酚动力学的影响,并通过光谱表征手段探讨了腐殖酸影响高锰酸钾氧化苯酚的作用机制.结果表明,黑腐酸对高锰酸钾氧化苯酚的促进作用明显高于黄腐酸,二者最高可将苯酚去除率从54.6%提高至95.3%和79.0%.腐殖酸中的醌基、酚基基团对氧化都有促进作用;而芳香族脂肪酸、葡萄糖和氨基酸基团则对氧化速率无影响.红外光谱分析表明,黑腐酸比黄腐酸含有更多的醌基和酚基结构,因此黑腐酸对高锰酸钾氧化苯酚动力学的促进程度更大.     

Fenton法处理垃圾渗滤液过程中有机物分子质量分布和荧光特性

采用Fenton氧化工艺对上海某垃圾填埋场垃圾渗滤液进行处理. 提取和分离了Fenton氧化前后腐殖酸组分(富里酸、胡敏酸),运用凝胶色谱法和三维荧光光谱技术对Fenton氧化前后各物质的分子质量分布和有机物荧光特性进行了研究. 结果表明:Fenton反应可使ρ(BOD₅)/ρ(COD_Cr)从0.011提高到0.285. 通过分子质量分布和三维荧光特性的测量可知,造成这种可生化性提高的原因是Fenton反应使垃圾渗滤液中有机物的分子质量降低,其中对高分子质量胡敏酸的去除以及对富里酸分子质量的降低起到了关键作用.      

接种外源微生物生活垃圾堆肥中的胡敏酸荧光特性

利用城市生活垃圾接种外源微生物,采用工厂化工艺进行堆肥,对堆肥前后胡敏酸荧光光谱进行了分析．结果表明,胡敏酸发射光谱相对简单,在440nm附近形成1个较宽的谱带,而激发光谱与同步扫描光谱则由几个特征峰及肩峰组成．对不同荧光光谱特征峰的分析表明,堆肥结束后,胡敏酸的腐殖化程度明显增加．CK、MS、ZJ、MS＋ZJ各处理的荧光光谱形状基本相似,但主要特征峰的相对荧光强度有明显区别．其中接种外源微生物可明显增加堆肥胡敏酸分子的缩合度,中加酵素菌（ZJ）处理优于美商复合菌（MS）处理,而2种外源菌混合接种具有协同促进作用．通过与土壤中胡敏酸荧光特性比较证实,堆肥后的胡敏酸具有土壤富里酸的特征,活性较高．     

滇池流域土壤活性腐殖质及其主要组分的紫外-可见与三维荧光光学特性

利用紫外-可见光谱和三维荧光光谱技术,结合土壤腐殖质及腐殖质组分(胡敏酸、富里酸)中的有机碳含量,研究了滇池流域土壤活性腐殖质及其组分胡敏酸和富里酸的光谱特征.结果表明,滇池流域土壤活性腐殖质中富里酸含量高于胡敏酸,流域范围内土壤活性腐殖质及其组分含量分布不均匀,活性腐殖质、胡敏酸和富里酸含量的变异系数分别达37.7%、36.4%、40.9%.土壤活性腐殖质及其组分胡敏酸和富里酸的碳含量均表现为菜地荒地草地湿地.光谱特征结果表明,滇池流域土壤活性腐殖质主要由自生源物质和经一定程度降解后的外源物质共同组成.此外,自生源性与光化学及生物活性具有正相关关系.因此,具有弱自生源性的滇池流域土壤活性腐殖质所具有的光化学和生物活性较弱.     

多环芳烃（PAHs）在不同腐殖酸组分中的赋存特征和氧化降解效果研究

选取腐殖酸重要组分胡敏酸、富里酸、胡敏素为研究对象,研究了不同老化时间下多环芳烃(PAHs)在腐殖酸各组分中的赋存特征.同时,探究了过硫酸钠、高锰酸钾、芬顿试剂、过氧化氢4种氧化剂氧化PAHs过程中污染物在腐殖酸和上清液中的分布情况,确定胡敏酸、富里酸、胡敏素中PAHs的降解效率.实验结果表明,PAHs在胡敏素中存在吸附滞后现象,老化前期胡敏素对PAHs的吸附速率慢、吸附量少,但老化后期出现吸附量的反超,因此,胡敏素、胡敏酸和富里酸中PAHs的最终吸附量并没有明显差异.高环PAHs在3种腐殖酸组分中的吸附速率和最终吸附量远小于低、中环PAHs.过硫酸钠和高锰酸钾能够较好地去除胡敏酸、富里酸、胡敏素中的大部分PAHs,去除率均在95%左右,芬顿试剂对胡敏酸、富里酸和胡敏素中总PAHs的去除效果差别不大,去除率均在79.36%~88.05%之间;过氧化氢对胡敏酸和胡敏素中PAHs的去除率分别为82.82%和61.77%,而对富里酸中PAHs的去除效果最差,去除率仅为43.96%.过硫酸钠和高锰酸钾是氧化PAHs类有机污染土壤的最佳氧化剂,能够有效提高不同组分腐殖酸中PAHs的去除率.     

牛粪生物堆肥有机酸变化及对腐熟度的影响

利用外源微生物(发酵菌,EM)进行牛粪工厂化堆肥,堆肥期间,分析了小分子有机酸及大分子腐殖酸动态变化。结果表明,接种外源微生物可明显提高堆肥前期小分子有机酸含量,在堆肥后期又呈明显降低的趋势;腐殖酸呈先降低而后趋于稳定的趋势,胡敏酸呈先降低而后增加的趋势,富里酸呈一直下降的趋势。对堆肥过程中有机酸、腐殖化指数分析表明,接种外源微生物可明显提高堆肥的腐熟度,但与微生物添加量有关。     

某冶炼厂周边土壤碳组分与铜形态的相关性

研究了浙江某冶炼污染区农田土壤有机碳组分与铜(Cu)形态的相关关系.结果表明,研究区土壤Cu形态含量为铁锰氧化物结合态残渣态碳酸盐结合态有机质结合态可交换态,其中铁锰氧化物结合态Cu和残渣态Cu含量分别占全量的39.55%和39.19%.土壤p H值和碳组分对不同形态Cu含量存在一定程度的影响,其中p H值与碳酸盐结合态Cu和铁锰氧化物结合态Cu均呈显著正相关;溶解性有机碳(DOC)含量与可交换态Cu呈极显著正相关;富里酸(FA)含量与可交换态Cu呈极显著正相关,与有机结合态Cu呈显著正相关;胡敏酸(HA)含量分别与可交换态Cu和有机结合态Cu呈极显著正相关.土壤DOC、FA、HA的动态变化对这些在移动性上存在差异的Cu形态间的相互转化会带来一定程度的影响,从而改变土壤Cu的迁移能力和生物有效性.     

基于非对称场流分离技术的水环境腐殖酸聚集特性研究

腐殖酸的聚集特性是影响其去除率及与其它污染物相互作用的重要因素,本文采用非对称场流分离技术对腐殖酸组分进行分离,配合示差折光检测器及多角度激光光散射器,对腐殖酸分子量的分布规律进行研究,探讨了水环境的化学条件对腐殖酸荷电状态和聚集状态的影响规律.结果表明,腐殖酸具有自我凝聚的特性;在p H较低和溶液离子强度较高时,腐殖酸胶粒的Zeta电位绝对值减小而分子量增大,腐殖酸胶粒聚集程度增大;随腐殖酸浓度增大,腐殖酸胶粒的Zeta电位绝对值减小,腐殖酸分子发生聚集而使胶粒分子量增大.当离子强度达到0.08mol·L-1,或浓度达到15 mg·L-1时,腐殖酸分子不仅靠氢键聚集在一起,还可能发生分子间的缔合.     

强化混凝对腐殖酸和富里酸去除对比研究

以腐殖酸和富里酸为研究对象,考察了硫酸铝、三氯化铁、聚合氯化铝和聚合氯化铁这4种混凝剂的强化混凝效果,并研究了pH、浊度及Ca2+、腐殖酸和富里酸相对含量对强化混凝的影响.结果表明,4种混凝剂对腐殖酸的去除效果要高于富里酸,三氯化铁和硫酸铝比聚合氯化铝和聚合氯化铁具有更好的混凝效果,在混凝剂投量为40 mg.L-1时,三氯化铁、硫酸铝、聚合氯化铁和聚合氯化铝混凝后可将水样中富里酸浓度由10 mg.L-1分别降为3.22、4.34、5.85和4.86 mg.L-1,而腐殖酸浓度可分别降至1.13、2.13、3.44和2.50 mg.L-1.三氯化铁和硫酸铝强化混凝的最佳pH为5.5～6.5,在其它pH范围强化混凝效果降低;水样中有机物浓度越高,混凝效果越差,富里酸/腐殖酸>0.4后混凝效果明显变差.浊度对混凝剂去除有机物的影响较小,Ca2+浓度的增加可提高腐殖酸和富里酸的去除效果.     

吉林省土壤中腐殖酸和水溶性富里酸分布特征与大骨节病关系的研究

本研究测定了吉林省主要土类样品中腐殖酸、富里酸的含量及水溶性富里酸的释放量,并研究其概率分布类型和水溶性富里酸的释放量与富里酸含量、深度、类型的关系。结果表明,土壤富里酸的释放量与大骨节病病情呈明显的正相关(r=0.845,P<0.05)。提出饮用富里酸释放量最高的O_2、Q_3层地下水,是引起平原地区大骨节病的可能因素。     

Effects of advanced oxidation pretreatment on residual aluminum control in high humic acid water purification

Due to the formation of disinfection by-products and high concentrations of Al residue in drinking water purification, humic substances are a major component of organic matter in natural waters and have therefore received a great deal of attention in recent years. We investigated the effects of advanced oxidation pretreatment methods usually applied for removing dissolved organic matters on residual Al control. Results showed that the presence of humic acid increased residual Al concentration notably. With 15 mg/L of humic acid in raw water, the concentrations of soluble aluminum and total aluminum in the treated water were close to the quantity of Al addition. After increasing coagulant dosage from 12 to 120 mg/L, the total-Al in the treated water was controlled to below 0.2 mg/L. Purification systems with ozonation, chlorination, or potassium permanganate oxidation pretreatment units had little effects on residual Al control; while UV radiation decreased Al concentration notably. Combined with ozonation, the effects of UV radiation were enhanced. Optimal dosages were 0.5 mg O3/mg C and 3 hr for raw water with 15 mg/L of humic acid. Under UV light radiation, the combined forces or bonds that existed among humic acid molecules were destroyed; adsorption sites increased positively with radiation time, which promoted adsorption of humic acid onto polymeric aluminum and Al(OH)3(s). This work provides a new solution for humic acid coagulation and residual Al control for raw water with humic acid purification.     

Factors effecting aluminum speciation in drinking water be laboratory research

Effects of aluminum on water distribution system and human health mainly attribute to its speciation in drinking water. Laboratory experiments were performed to investigate factors that may influence aluminum speciation in water supply system. The concentration of soluble aluminum and its transformation among other aluminum species were mainly controlled by kinetics processes of related reactions. Total aluminum concentration had a notable effect on the concentrations of mononuclear and soluble aluminum in the first 4 day; while, when the reaction time was above 4 day, its effect became weak. At pH above 7.50, both fluoride and orthophosphate had little effect on aluminum speciation; while, when the solution pH was below 7.50, the concentrations of mononuclear and soluble aluminum were proportional to the concentration of fluoride and inversely proportional to the concentration of orthophosphate. Both mononuclear and polynuclear silicic acids could complex with mononuclear aluminum by forming soluble aluminosilicates. In addition, the adding sequence of orthophosphate and aluminum into drinking water would also affect the distribution of aluminum species in the first 4 day. In order to minimize aluminum bioavailability in drinking water, it was suggested that orthophosphate should be added prior to coagulant process, and that the concentrations of fluoride and silicic acids be controlled below 2.0 and 25 mg/L, respectively, prior to the treatment. The solution pH in coagulation and filtration processes should be controlled in the range of 6.50-7.50.     

Factors effecting aluminum speciation in drinking water by laboratory research

Effects of aluminum on water distribution system and human health mainly attribute to its speciation in drinking water. Laboratory experiments were performed to investigate factors that may influence aluminum speciation in water supply system. The concentration of soluble aluminum and its transformation among other aluminum species were mainly controlled by kinetics processes of related reactions. Total aluminum concentration had a notable e ect on the concentrations of mononuclear and soluble aluminum in the first 4 day; then its e ect became weak. At pH above 7.50, both fluoride and orthophosphate had little e ect on aluminum speciation; while, when the solution pH was below 7.50, the concentrations of mononuclear and soluble aluminum were proportional to the concentration of fluoride and inversely proportional to the concentration of orthophosphate. Both mononuclear and polynuclear silicic acids could complex with mononuclear aluminum by forming soluble aluminosilicates. In addition, the adding sequence of orthophosphate and aluminum into drinking water would also a ect the distribution of aluminum species in the first 4 day. In order to minimize aluminum bioavailability in drinking water, it was suggested that orthophosphate should be added prior to coagulant process, and that the concentrations of fluoride and silicic acids should be controlled below 2.0 and 25 mg/L, respectively, prior to the treatment. The solution pH in coagulation and filtration processes should be controlled in the range of 6.50–7.50.     

Interaction of humic substances and hematite: FTIR study

IntroductionInteractionsofhumicsubstances(HSs)andironoxidesareofgreatsignificanceinmanygeochemicalprocesses.ItisclearthatadsorptionofHSstothesurfaceofironoxidescangreatlyinfluencethepropertiesofsuchsurfaces,thuspotentialaffectthefate,behavior,transportandtransformationofenvironmentalpollutants(Mcknight,1992).Ononehand,whenadsorbedtosurfacesofironoxides,HSsmaybindandhenceimmobilizetracemetals,radionucilides,andnonionicorganicpollutants,andtheyalsoalteroxidesurfacechargepropertiesandflocculat…     

Study on the effects of organic matter characteristics on the residual aluminum and flocs in coagulation processes

Characteristics of organic matter may affect the residual aluminum after the coagulation process. This study reported the results of a survey for one drinking water treatment plant and measured the concentration of residual aluminum species with different molecular weights. Survey results indicated that humic acid or organic matter whose molecular weight was smaller than 1500 Da had significant effects on residual aluminum. All the treatment processes were ineffective in removing dissolved organic matter whose molecular weight was smaller than 1500 Da. These results also indicated that the addition of sand or polyacrylamide in the coagulation process could greatly decrease the concentration of humic acid, and the concentration of residual aluminum also decreased. These results revealed that for all water samples after filtration, the majority of total residual aluminum existed in the form of total dissolved aluminum, accounting for 70%–90%. The concentration of residual aluminum produced in bovine serum albumin solutions indicated that when the DOC was larger than 4.0 mg/L, there were still significant differences when the solution pH value varied from 4.0 to 9.0.     

富里酸和胡敏酸在蒙脱石上的吸附特性

为进一步揭示有机污染物在黏土矿物上的迁移转化规律,运用1H核磁共振光谱、高效体积排阻色谱、扫描电镜、比表面分析以及傅里叶变换红外光谱等多种分析技术综合分析了富里酸和胡敏酸在蒙脱石上的吸附行为. 结果表明,由于不同官能团与蒙脱石的亲和性不同,富里酸和胡敏酸在吸附过程中均产生组分分级,大分子被优先吸附在蒙脱石表面. 由于疏水性作用,蒙脱石对疏水性更强的胡敏酸的吸附量更大. 蒙脱石吸附富里酸后比表面积和孔容分别下降3.67m2/g和0.005cm3/g,而吸附胡敏酸后则均略微增大,说明具有较大颗粒尺寸的胡敏酸更多地堆积在蒙脱石外表面,而富里酸则更易进入蒙脱石孔隙. 蒙脱石吸附富里酸和胡敏酸后溶液pH分别升高了0.44和0.41,说明发生了配体交换反应. 蒙脱石对富里酸和胡敏酸的吸附量随pH增大和离子强度的降低而减少,表明羟基能够抑制富里酸/胡敏酸负电基团与蒙脱石表面羟基的配体交换反应,而盐离子则能降低蒙脱石和腐殖质间的静电斥力.      

Cu2+在混凝中对富里酸氯化消毒副产物的影响

混凝实验采用硫酸铝作为混凝剂,以富里酸（FA）为目标物,考察Cu²⁺对浊度、溶解性有机碳（DOC）去除效果和氯化消毒副产物生成势（DBPsFP）的影响,并采用三维荧光光谱（3DEEM）和超滤膜分级对混凝出水进行表征.结果表明,Cu²⁺可以通过络合反应提高混凝过程对FA中亲水性组分和芳香结构DBPs前驱体的去除效果.在pH> 7时,可以使二氯乙酸生成势（DCAAFP）和三氯甲烷生成势（TCMFP）明显降低.Cu²⁺-混凝的作用更倾向于影响FA中分子量级分处于10~30kDa的物质,提高其对DOC和DBPs生成势的去除效果.     

秸秆生物质炭DOM光谱特征及其与Cu2+的相互作用

通过荧光猝灭滴定法探究玉米秸秆炭（MSB）、水稻秸秆炭（RSB）和花生秸秆炭（PSB）中DOM的光谱特征及其与Cu²⁺的络合机理.结果表明：三种生物质炭的DOM均具有较高的亲水性和较低的芳香性,其中RSB-DOM的芳香性相对较强、分子量较大,但DOM含量低,PSB-DOM含量最高,芳香结构中含氧官能团较多.MSB和RSB-DOM中均含类富里酸组分C1和类腐殖酸组分C3、C4,RSB-DOM中还有类色氨酸组分C5,PSB-DOM则由两种类富里酸组分C1、C2和较长波长类腐殖酸组分C4组成,3种DOM均以类富里酸组分为主,占比达54.93%~86.29%.Cu²⁺与类腐殖酸组分的稳定常数（logK_M）高于类富里酸组分,且类腐殖酸组分C4的络合能力（f）最强,类腐殖酸组分的logK_M和f值总体上表现为：PSB-DOM> MSB-DOM>RSB-DOM.二维相关光谱分析发现,类富里酸组分对Cu²⁺最敏感,而Cu²⁺优先与类腐殖酸组分结合.研究结果有助于进一步揭示生物质炭的DOM对Cu²⁺环境行为的影响机制.