土壤腐殖质氧化还原电位及其相应电子转移能力分布

本实验以土壤提纯腐殖酸及国际标准腐殖酸(Pahokee Peat Humic Acid,PPHA)为研究对象,测定腐殖酸与3种不同氧化还原Eh的铁矿物(水铁矿(Ferrihydrite)Eh0'=0 m V,赤铁矿(Fe2O3)Eh0'=-287 m V,磁铁矿(Fe3O4)Eh0'=-314 m V及溶解性铁铁氰化钾Eh0'(Ferricyanide=+430 m V)的氧化还原反应,结合Eh-p H计的实验体系,分析腐殖质分子氧化还原官能团的分布规律.磁铁矿同时拥有二价和三价铁离子,具有与腐殖质发生氧化或者还原反应的条件.不同土壤腐殖酸与磁铁矿反应表现的还原/氧化能力不同,这是由于腐殖酸的不同Eh引起,在此基础上测量显示原态下腐殖酸Eh值大约为245 m V,H2还原后,Eh值降低至-620 m V,表明腐殖酸的氧化还原Eh是不同种类和数量的氧化还原官能团Eh叠加值.分析标准腐殖酸在不同氧化还原Eh下的氧化/还原能力显示原态下标准腐殖酸的氧化还原Eh分布比较均匀,还原态腐殖酸在Eh0范围存在易于被氢气还原的官能团,具有显著的还原能力.     

城市污水活性污泥处理系统中有机物分子量的分布及其变化

利用凝胶过滤色谱法对某城市污水处理系统(缺氧/好氧,A/O活性污泥法)中有机物的分子量在水相和胞外聚合物(EPS)中的分布及其变化进行研究.结果表明:污水处理过程中分子量的分布沿程变窄,对分布在各段分子量之间的有机物都有大幅度的去除;缺氧池和好氧池的EPS中都有14%的物质分子量大于1000万,而水相中各类物质的分子量均小于200万,说明该类大分子的EPS并非因吸附而成.     

川牛膝多糖的分离、纯化及单糖组成

采用水提醇沉法提取川牛膝多糖粗品CPC，经685弱碱阴离子交换柱层析和Bio—Gel P2凝胶柱层析进一步纯化，得到川牛膝多糖RCP(xefined Cyathula officinalis Kuan polysaccharide)．紫外扫描、高效液相色谱、聚丙烯酰胺盘状凝胶电泳证明RCP为均一组分．质谱图显示RCP的分子量(从)主要分布在1000-2200．薄层正交试验确定了RCP完全水解的最优条件．薄层层析及高效液相色谱—蒸发光散射检测(HPLC—ELSD)技术揭示，RCP单糖组成为D-果糖和D-葡萄糖．图11表2参18     

分子结构在腐殖酸对菲吸附行为中的影响

用连续碱提取具有不同结构组成特征的腐殖酸级分,考察了分子结构在腐殖酸对菲吸附行为中的影响,结果表明：随着腐殖酸中元素碳、表观分子量以及脂肪碳含量的增加,腐殖酸对菲的吸附能力和吸附的非线性特征都呈增强趋势;相反,随着腐殖酸中元素氧和芳香碳含量的增加,腐殖酸对菲的吸附能力和吸附的非线性都逐渐减弱,这主要与结构中极性官能团所连位置有关．     

硅胶色层分析土壤中水溶性腐殖酸

采用水浸取法和硅胶色层法，通过紫外吸收光谱峰定性鉴定了英格兰七种土壤水溶性腐殖酸。沉积土中水溶性腐殖酸均展示了二组峰值，而在草原土中低分子量组份消失。选用γ谱仪测定了沉积土水溶性腐殖酸中的放射性核素^137Cs，采用中子活化测量技术分析了常量钠和氯。结果表明，在高盐含量的沉积土中存在的大量竞争络合离子钠可能是使放射性核素^137Cs与沉积土中水溶性腐殖酸没有直接关系的原因。     

腐殖酸存在下镉和铅对土壤脱氢酶活性的影响

采用室内培养试验研究Cd和Pb污染红壤添加不同组分腐殖酸后,其脱氢酶活性的变化,结果表明,红壤遭受镉和铅污染后,脱氢酶活性显著降低,然而腐殖酸特别是胡敏酸的存在能够使脱氢酶活性得到显著回升,说明腐殖酸与重金属的相互作用对重金属污染土壤微生物活性的改善和修复功能,对土壤有一定的去污降毒作用.不同腐殖酸组分的效应大小为:灰色胡敏酸(GHA)>棕色胡敏酸(BHA)>富里酸(FA),表明分子量愈大、芳构化程度愈高的腐殖酸组分,其对重金属的钝化愈强,从而解除土壤重金属对生物毒害的能力愈强.     

美国红鱼卵黄原蛋白的分离纯化及电泳性质鉴定

腹腔注射0.02mg/gBW17β-雌二醇,诱导美国红鱼1wk后取尾静脉血,离心分离得到的血浆经Sephacryl S-300 high resolution分子筛分离、纯化卵黄原蛋白.常规聚丙烯酰胺凝胶电泳的考马斯亮蓝染色和糖、磷、脂的特征性基团染色结果表明,17β-雌二醇诱导美国红鱼产生了两种形式的卵黄原蛋白,以Native-PAGE方法计算出美国红鱼两种卵黄原蛋白的分子量分别为344×103和247×103,以SDS-PAGE方法得出卵黄原蛋白3种亚基的分子量为152×103、133×103和118×103.分子筛凝胶过滤能较好地分离纯化美国红鱼血浆中的卵黄原蛋白.图8参17     

蚯蚓生物处理对剩余污泥腐殖酸特性的影响

以城市污水处理厂产生的剩余污泥为对象,研究蚯蚓(赤子爱胜蚓)生物处理对剩余污泥腐殖酸相关性质的影响.结果表明,在水力负荷4.0 m3·m-2·d-1、有机负荷1.70 kgVSS·m-3·d-1的条件下,蚯蚓生物滤池对于剩余污泥具有良好的减量化效果,VSS平均减量率为55.2%.随着蚯蚓滤池反应器高度的增加,处理后污泥中腐殖酸的C/H值、E4/E6(465 nm与665 nm吸光度的比值)值逐渐降低,紫外光谱205—210 nm处最大吸收峰向近紫外区移动,腐殖酸分子量增大,芳构化明显,缩合程度加强,出泥腐殖化程度提高.荧光淬灭实验分析显示腐殖酸与重金属Cu(Ⅱ)的络合作用明显,蚯蚓滤池处理出泥腐殖酸的络合容量相对进泥有所增加,可溶性铜离子含量降低,可能减少被作物吸收的风险.     

铬离子对序批式好氧生物反应器出水中溶解性微生物产物的影响

考察了序批式好氧生物反应器(SBR)中,重金属铬离子对溶解性微生物产物(SMP)总量、分子量分布及其组成中多聚糖、蛋白质和DNA含量的影响.铬离子的生物容许浓度在2mg·l-1之下,SMP总量与铬离子浓度存在指数关系:SMP=24.94e0.593C.SMP的分子量呈双峰分布,且分子量小于1kDa的部分基本上占50%以上.SMP中的DNA含量随铬离子浓度的增加而降低,在显著水平α=0.05时,DNA含量与铬离子浓度呈线性相关.     

城市污水厂剩余污泥中腐殖酸化学组成与结构特征

采用元素分析、傅里叶红外光谱、固体~(13)C核磁共振以及三维荧光光谱技术,对不同污水处理厂剩余污泥中腐殖酸的化学组成和结构特征进行对比分析.结果表明,不同腐殖酸的化学组成极其相似,但在结构特征上存在明显差异.元素分析计算结果发现,不同腐殖酸的H/C、O/C和C/N的比值存在差异,说明其结构存在差异.荧光光谱显示各个腐殖酸均存在两个明显的特征峰.荧光指数表明各个腐殖酸均为生物源腐殖酸,与元素分析测得的H/C结论一致.傅里叶红外分析显示A厂腐殖酸的各个官能团吸收峰最大、即各个官能团含量最多,C厂含有最少的含氧官能团.13C-NMR结果表明,A厂腐殖酸含有最多的脂肪碳和芳香碳结构,而D厂腐殖酸与之相反.     

High amounts of free aromatic amino acids in the protein-like fluorescence of water-dissolved organic matter

Fluorescence spectroscopy is widely used to study water pollution. The fluorescence of water natural organic matter can be classified into two groups: the protein-like fluorescence originating from aromatic amino acids and the humic fluorescence originating from humic substances. Actually, the precise molecular origin of the protein-like fluorescence is unknown because this fluorescence may be caused by either free amino acids, peptides or proteins. Therefore, we studied the molecular origin of the protein-like fluorescence of Suwannee River natural organic matter and fractions A, B and C + D obtained by size exclusion chromatography/polyacrylamide gel electrophoresis. Fractions were analyzed by reversed-phase high-performance liquid chromatography. The electrophoretic mobilities of fractions varied in the order C + D > B > A and the molecular size in the opposite order. Our results show that the protein-like fluorescence is almost exclusively located in high molecular size fraction A and medium molecular size fraction B. Retention times and fluorescence emission spectra of authentic free aromatic amino acids tyrosine and tryptophan were identical with the retention times and emission spectra of several chromatographic peaks of fractions A and B. More than 50 % of the protein-like fluorescence is due to free aromatic amino acids incorporated in water natural organic matter.     

土壤性质对土壤中汞赋存形态的影响

土壤是一个复杂的生态系统,典型相关分析表明,土壤的组成性状对土壤中汞的形态分布影响较大,影响因子主要有ＦＡ,ＨＡ,有机质和碳酸盐含量,土壤粘粒作用较小,土壤有机质表现出很强的表面络合能力。     

近地面O_3含量升高条件下土壤中腐殖质单体儿茶酚转化的放射性~（14）C示踪研究

近地面大气臭氧（O3）含量不断升高对生态环境的影响已引起人们的广泛关注,然而O3含量升高对土壤有机碳的矿化及转化影响却少有研究。土壤有机碳是全球碳循环的重要组成部分,土壤碳库的微小变化将引起大气CO2浓度的显著改变。文章以典型土壤腐殖质单体化合物儿茶酚为代表,利用14C示踪技术,研究了O3含量比当前背景升高约0.15μmol·mol-1时对土壤中腐殖质苯酚类前体化合物的矿化及转化的影响。结果表明,O3含量升高会对土壤中培育12d后儿茶酚的矿化及残留物分布具有显著的影响,而且这种影响程度和规律同土壤有关。O3含量升高促进了黄棕壤中儿茶酚的矿化,增加了儿茶酚残留物在黄棕壤腐殖酸（HA）中的总量,并使残留物在HA中偏向于同大分子结合。O3含量升高对灰潮土中儿茶酚的矿化有抑制作用,但对儿茶酚残留在HA内总量及分布没有显著影响。O3含量升高对儿茶酚在土壤中的稳定性及归趋的影响可能是O3对于微生物活性的抑制作用和O3的直接氧化作用的共同结果。后续工作中应研究土壤腐殖质中其它组份的稳定性及转化对近地面大气O3含量升高的响应,以全面考察O3含量升高对土壤碳库的影响。     

垃圾渗滤液中有机物分子量的分布及在MBR系统中的变化

利用凝胶层析方法分析了垃圾渗滤液中有机物分子量的分布情况,并考察了利用膜生物反应器(MBR)处理垃圾渗滤液系统中有机污染物分子量的分布以及水溶性腐殖质(AHS)含量的变化．研究发现,垃圾渗滤液中的有机物主要由两部分组成,即分子量大于6000的大分子物质和分子量小于1500的小分子物质．大分子物质主要是水溶性腐殖质,而小分子物质主要由挥发性有机酸及水溶性腐殖质组成．大分子的AHS难以被微生物降解,但能被微滤膜截留．大部分小分子的AHS既难以被微生物降解,又不能被膜截留,是构成MBR处理出水COD的主要成分．     

Dissolved Organic Matter in Forest Soils: Sources, Complexing Properties and Action On Herbaceous Plants

Dissolved organic matter (DOM) is an important component of plant-soil systems. Its essential role in soil solution chemistry, soil-forming processes and its effects on biota, including soil fauna, bacteria, fungi and plants, is extensively documented in literature. in this contribution several forest leaf litter types are compared as sources of DOM and the released organics are subjected to gel permeation chromatography to reveal their molecular-size distribution. Moreover, complexing properties, as an indication for the podzolization potential of the litter leachates, were established. the occurrence and properties of DOM in different soil horizons were monitored beneath a stand of Scots pine. the effects of the different groups of soluble organics including phenolic, fulvic and humic acids, and of water-extractable humic substances on the performance of herbaceous plants of the forest floor are briefly reviewed.     

腐殖质的光化学降解及其对环境污染物环境行为的影响

腐殖质是地表环境中最重要的有机组分,也是生态环境中最主要的吸光物质之一,对环境污染物的形态、迁移、毒性和生物可利用性有着重要的影响。文章综述了腐殖质的结构特征和光化学降解反应过程和机理,指出腐殖质的光敏化和光化学降解过程对环境污染物的环境行为和归宿有重要的影响。通常,腐殖质的光敏化作用在低质量浓度下,尤其在一定铁离子的协同作用下可促进有机污染物的降解,但高质量浓度的腐殖质由于其本身的吸光作用以及参与自由基的竞争则抑制有机污染物的降解。腐殖质的光化学降解过程降低了环境体系的pH和腐殖质的分子量、破坏了腐殖质的芳环结构、改变了紫外和可见光区域的吸收等,导致其与重金属离子和有机污染物结合能力的下降,造成水体或颗粒态中游离的污染物质量浓度增加,对生态系统将造成更大的危害。目前对腐殖质和环境污染物本身的光化学降解机理已较为清晰,今后应加强对自然水体或土壤系统中腐殖质光化学降解的影响因素,腐殖质光化学降解过程中结构特性的变化机理,以及腐殖质的结构特性与环境污染物结合性质之间的构效关系等方面的研究。特别是随着平流层臭氧空洞的增加,增强了到达地球表面的紫外线强度,研究紫外线增强对腐殖质和有机污染物的降解以及对生态系统的影响可进一步深刻理解太阳光辐射对污染物环境行为和归宿的影响。     

Rapid incorporation and short-term distribution of a nonylphenol isomer and the herbicide MCPA in soil-derived organo-clay complexes

Organo-clay complexes in soil are a major sink for xenobiotics and, thus, often enhance their persistence dramatically. However, the knowledge on environmental processes of non-extractable residue formation on a short time scale is very restricted. Therefore, this study examined the distribution of 4-(3,5-dimethylhept-3-yl)phenol (NP) and 4-chloro-2-methylphenoxyacetic acid (MCPA) in soil over a short time period of 48 h and in different soil sub-fractions. The overall proportion of organo-clay-associated bound residues was not only abundant but also in the same range for both substances (MCPA: 8%; NP: 11% of applied ¹⁴C-radioactivity). However, a more detailed view revealed two different distribution patterns: a higher proportion of clay-associated NP was accompanied by a lower content of bound residues, whereas a smaller fraction of clay-associated MCPA was characterized by a higher proportion of non-extractable residues. Further on, a selective accumulation of bound residues among clay-associated humic fractions was observed. NP residues were linked predominantly to humic acids, whereas MCPA residues tended to be incorporated more into fulvic acids. It was evident that the overall distribution was influenced primarily by the physico-chemical properties of the contaminants. This study demonstrates in detail a rapid initial incorporation accompanied by a specific distribution into soil sub-fractions for selected xenobiotics in soil and points to a complex interaction of clay-associated organic matter with low molecular weight compounds.     

Effect of natural aquatic humic substances on the photodegradation of bisphenol A

The photochemical degradation of bisphenol A (BPA) was studied in the presence of natural humic substances from different origins under simulated solar irradiation. BPA underwent insignificant direct photolysis in neutral water, but rapid photosensitized degradation in four humic substances solutions via pseudo-first-order reaction occurred. The photo-degradation rate of BPA was insensitive to the different initial BPA concentrations and was inhibited in aerated solution compared with the deoxygenated medium. The reactive oxygen species (ROS) such as ·OH and ¹O₂ produced from excitation of humic substances under irradiation was determined from the quenching kinetic experiment using molecular probe. The five main intermediate photoproducts of BPA in Nordic lake fulvic acid (NOFA) were tentatively identified using gas chromatography/mass spectrometer (GC/MS). Based on the identification of ROS and the analysis of photoproduct formation, the possible phototransformation pathways of BPA were proposed, involving the direct photolysis due to the energy transfer from the triplet state humic substance (³HS*) to BPA molecules and hydroxyl radical addition and oxidation as well.     

Huminstoffe in Sedimentporenwässern ausgewählter Bundeswasserstraßen

Humic substances are an important component of organic carbon in natural waters. Their character and properties are determined by the sources and the processes of their origin. Humic substances are not exclusively refractory compounds, but they are involved in several transformation processes in the water. It is not possible to directly analyze humic substances, therefore several methods were applied for their characterization. The presented LC-OCD-technique is a size-exclusion-chromatography with online UV- and carbon detection. Carbon fractions, e.?g. humic substances were differentiated by their molecular size. The portion of humic substances in sediment porewaters of the rivers Elbe, Rhine, Danube, Oder, Müritz-Elde-Waterway was determined. With only a few exceptions it ranges from 50 to 67?% of the dissolved organic carbon. The high molecular weight fraction accounts for 10 to 34?%, and the fraction of the low molecular weight substances was from 7 to 37?%. The ratio between the spectral absorption coefficient (254?nm) and the organic carbon is called SUVA (L/mg × m) and is an inidicator of the proportion of unsaturated bonds in the humic substances. Both high molecular herbal components (e.?g. cellulose, lignin) and biological degradiation products (e.?g. amino acids, sugar) are involved in sediment porewater transformation and degradiation processes. This demonstrates the distribution of the dissolved organic carbon between the fractions.