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.     

水中天然含氮有机物的形成、迁移转化及分布

天然含氮有机物是水环境中的重要组成部分,其在天然水体中的形态及分布对环境质量有显著影响.本文围绕水中天然含氮有机物在氮循环中的地位、迁移转化以及其在国内主要水域中的分布情况,对天然含氮有机物的研究现状进行了梳理.我国不同水域中溶解性含氮有机物(DON)浓度相差较大;其中水体中DON浓度一般在1.0 mg?L-1以下;沉...     

Isolation and Chemical Characterization of Dissolved and Colloidal Organic Matter

An overview of the methods used for the isolation and characterization of organic matter in natural waters is presented. Commonly used techniques for the concentration and isolation of organic matter from water, such as preparative chromatography, ultrafiltration and reverse osmosis, and the methods used to analyze the organic matter obtained by these methods are reviewed. the development of methods to obtain organic matter that is associated with fractions of the dissolved organic carbon other than humic substances, such as organic bases, hydrophilic organic acids and colloidal organic matter are discussed. Methods specifically used to study dissolved organic nitrogen and dissolved organic phosphorous are also discussed.     

Isolation and Chemical Characterization of Dissolved and Colloidal Organic Matter

An overview of the methods used for the isolation and characterization of organic matter in natural waters is presented. Commonly used techniques for the concentration and isolation of organic matter from water, such as preparative chromatography, ultrafiltration and reverse osmosis, and the methods used to analyze the organic matter obtained by these methods are reviewed. the development of methods to obtain organic matter that is associated with fractions of the dissolved organic carbon other than humic substances, such as organic bases, hydrophilic organic acids and colloidal organic matter are discussed. Methods specifically used to study dissolved organic nitrogen and dissolved organic phosphorous are also discussed.     

UV light induces Ag nanoparticle formation: roles of natural organic matter,iron, and oxygen

Nanoparticles occurring in the environment originate either from engineered, synthetically produced nanoparticles, or from naturally produced nanoparticles. The latter can be formed in natural media by light-induced reduction of metal ions in presence of natural organic matter, such as humic substances occurring widely in waters, soils and sediments. There is actually few knowledge on the effect of sunlight and of the nature of organic matter on nanoparticle formation. Therefore, we studied here the photoreduction of silver(I) ion to silver nanoparticles with and without ferrous ion under oxic and anoxic conditions, using humic and fulvic acids as proxies of natural organic matter. UV light-induced formation of silver nanoparticles was monitored up to 60 min by measuring surface plasmon resonance in air-saturated mixture and nitrogen-saturated mixture of silver(I) ion–organic matter. Results show that the surface plasmon resonance intensity was about 2.5 times higher in the nitrogen-purged solution mixture than the air-saturated solution. This finding suggests the oxygen-containing species had no major role in forming silver nanoparticles. Therefore, photo-driven formation of silver nanoparticles most likely involved photoactivation of silver(I) ion and natural organic matter complexes. We observed also that both iron(II) and iron(III) ions highly modified the surface plasmon resonance spectra of the particles with broader features. Results also reveal that in the presence of humic acid, the intensity of the surface plasmon resonance peak decreased by at least 50 %, while almost no change in the intensity was seen when fulvic acid was used. Overall, our findings demonstrate that the ligand–metal charge transfer process, affected by the nature of organic matter, i.e., humic acid versus fulvic acid, was influenced by redox iron species.     

Enhanced degradation of trichloroethylene using bentonite-supported nanoscale Fe/Ni and humic acids

Nanoscale zero-valent iron, named nano-Fe⁰, is a reagent used to degrade trichloroethylene in groundwater. However, the efficiency of nano-Fe⁰ is moderate due to issues of dispersion and reactivity. As an alternative we synthesized bentonite-supported nanoscale Fe/Ni bimetals, named bentonite-Fe/Ni, to test the degradation of trichloroethylene in the presence of Suwannee River humic acids, as a representative of natural organic matter. 0.1 mmol/L trichloroethylene was reacted with 0.5 g/L of nano-Fe⁰, bentonite-Fe, Fe/Ni, and bentonite-Fe/Ni nanoparticles. Results show first that without humic acids the reaction rate constants k _obs were 0.0036/h for nano-Fe⁰, 0.0101/h for bentonite-Fe, 0.0984/h for Fe/Ni, and 0.181/h for bentonite-Fe/Ni. These findings show that bentonite-Fe/Ni is the most efficient reagent. Second, the addition of humic acids increased the rate constant from 0.178/h for 10 mg/L humic acids to 0.652/h for 40 mg/L humic acids, using the bentonite-Fe/Ni catalyst. This finding is explained by accelerated dechlorination by faster electron transfer induced by humic quinone moieties. Indeed, the use of 9, 10-anthraquinone-2, 6-disulfonate as a humic analogue gave similar results.     

Photoreactivity of humic substances: relationship between fluorescence and singlet oxygen production

Humic substances are natural compounds abundantly present in the environment. They play a significant role in the natural attenuation of pollution in surface water due to their capacity to generate reactive species upon solar light excitation. Finding physico chemical parameters related to this property would be of a great help in the prediction studies of the organic pollutants fate. In this work, we investigated relationships between the ability of the humic substances to produce singlet oxygen and their fluorescence properties. For this, a series of sixteen humic acids, fulvic acids, and water-extractable organic matter from soils were studied. The steady-state singlet oxygen concentrations in the irradiated humic substances solutions were measured by monitoring the loss of furfuryl alcohol added as a singlet oxygen scavenger. The emission spectra of the sixteen samples were also recorded. Values of the steady-state singlet oxygen concentrations and the emission intensities showed significant variations among the humic samples and a parallel increase. Thus, here we demonstrate that the rate of singlet oxygen production and the emission intensity of the humic samples are correlated, the best correlation being obtained for emission wavelengths between 500 and 580 nm. This correlation which was never reported until now can be used to estimate the singlet oxygen-production capacity of the humic substances based on their fluorescent properties.     

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.     

Variation in humic and fulvic acids during thermal sludge treatment assessed by size fractionation,elementary analysis,and spectroscopic methods

Thermal pretreatment can be applied to sludge anaerobic digestion or dewatering. To analyze the variation in humic substances during thermal sludge treatment, sludge humic and fulvic acids were extracted before and after 30-min thermal treatment at 180℃, and then their contents, molecular weight distributions, elementary compositions, and spectral characteristics were compared. The results showed that the total contents of humic and fulvic acids in the sludge almost remained constant during thermal treatment, but 35% ofhumic and fulvic acids were dissolved from the sludge solids. Moreover, both humic and fulvic acids were partly decomposed and 32% of humic acids were converted to fulvic acids. The median value of the molecular weights of humic acids decreased from 81 to 41 kDa and that of fulvic acids decreased from 15 to 2 kDa. Besides the reduction in molecular size, the chemical structures of humic and fulvic acids also exhibited a slight change, i.e. some oxygen functional groups disappeared and aromatic structures increased after thermal sludge treatment.     

氯化消毒饮用水中强致突变物MX[3-氯-4-(二氯甲基)-5-羟基-2(5H)-呋喃酮]的形成

利用一系列XAD吸附树脂及大孔阴、阳离子交换树脂,将太湖水中溶解态有机物分离为溶解态富里酸类、腐殖酸类、憎水弱酸类、憎水碱类、憎水中性物类、亲水酸类、亲水碱类七种组分,分别对不同组分的有机物进行氯化处理后,用GC/MS选择离子峰面积法测定了产物中的MX[3-氯-4-（二氯甲基）-5-羟基-2（5H）-呋喃酮]。结果表明,太湖水体中的溶解态腐殖酸类可能是生成MX的重要前驱物。     

Diuron herbicide degradation catalyzed by low molecular weight humic acid-like compounds

Phenylureas such as diuron are major herbicides used worldwide to control undesirable weeds. The environmental fate of phenylureas is of great interest because massive amounts of those herbicides are used. It is known that abiotic degradation of phenylureas in soil–water systems is catalyzed by humic acids. However, due to the chemical heterogeneity and large molecular sizes of humic acids, the specific effects of functional groups during catalysis have not been elucidated. Therefore, we studied here for the first time the kinetics of diuron degradation in the presence of low molecular weight humic acid-like compounds such as benzoic acid derivatives. Experiments were carried out at various pH and temperature, and monitored by high-performance liquid chromatography. Results show that all benzoic acid derivatives efficiently catalyzed diuron hydrolysis. The catalytic efficiency decreased in the following order: 0.88 M^?1 day^?1 for 3,4-dihydroxybenzoic acid, 0.72 M^?1 day^?1 for 4-hydroxybenzoic acid, 0.23 M^?1 day^?1 for phthalic acid, 0.11 M^?1 day^?1 for 2-hydroxybenzoic acid, and 0.09 M^?1 day^?1 for 2,4-dihydroxybenzoic acid. These differences in the catalytic efficiency are explained by steric hindrance affecting the accessibility of reactive sites and hence influencing the rate of the overall process. Steric factors are therefore expected to control the catalytic activity of humic acids because of the chemical similarities between humic acids and low molecular weight humic acid-like compound. Our results should help predict more accurately the fate and abiotic degradation mechanism of phenylureas in the environment.     

Polyaniline films for efficient removal of aromatic acids from water

Adsorbents in the form of powders are commonly used to filtrate organic compounds in waters. However, this technique requires the separation of the solid phase from the solution after adsorption experiments. Here we propose the use of films as adsorbents. We synthesized polyaniline films by chemical oxidative polymerization of aniline on red ceramic brick. This film was tested to remove trimellitic, hemimellitic and pyromellitic acids as model molecules of the biodegradation of aquatic humic substances. We evaluated the effect of pH, contact time and initial concentration. Our results show that optimal adsorption conditions required 45 min of solid/liquid contact at pH 7 and an initial concentration of 20 mg/l. The maximum adsorption capacities for hemimellitic, trimellitic and pyromellitic acids are 154.83 for hemimellitic acid, 161.88 for trimellitic acid and 175.26 mg/g for pyromellitic acid. The adsorption efficiency of the polyaniline film decreased only by 13 % after four cycles. Overall, we conclude that polyaniline films are promising separable adsorbents compared to conventional adsorbents for removal of aromatic polycarboxylic acids from water.     

Three-dimensional fluorescence spectral characterization of soil dissolved organic matters in the fluctuating water-level zone of Kai County, Three Gorges Reservoir

Three-dimensional fluorescence spectroscopy was used to investigate the fluorescent properties of soil dissolved organic matter (DOM) in the water-level-fluctuation zone (WLFZ) of Kai County, Three Gorges Reservoir (TGR). Most of the soil DOM analyzed in this study was found to contain four fluorescence peaks. Peaks A and C represent humic-like fluorescence, whereas peaks B and D represent tryptophan-like fluorescence. Peaks E and F, which represent tyrosine-like fluorescence, only appeared in certain soils. Soil humus was the main source of DOM in soil, and higher concentration of soil DOM was found in the exposed soil than submerged soil. Compared to the peaks A and B, the fluorescence intensities of peaks C and D were strongly influenced by the fluctuating water level. Analysis of fluorescence intensities of different peaks in soil DOM showed that WLFZ soil was not contaminated significantly. Soil DOM contained at least two types of humic-like fluorescence groups and two types of protein-like fluorescence groups. The proportion of the content of peak A in soil organic matter was quite stable. The soil DOM in exposed soil had relatively high humification and aromaticity, and periodic submerging and exposure of soil had an impact on the humification of soil DOM.     

The role of organic matter components in soil on partitioning of Chlorohydrocarbons

Triolein, farnesol, humic acid, methyl salicylate, lignin and cellulose were selected as representative soil organic matter components. Equilibrium partition coefficients between these materials and water were experimentally determined for lindane, aldrin and a series of chlorobenzenes. Theoretical values for the chlorobenzenes were also determined using a Regular Solution Theory approach. The molecular size and polarity of the sorbent or organic matter components were identified as factors influencing the magnitude of the partition coefficient. Both experimental and theoretical partition coefficients were compared with soil/water values expressed on an organic matter basis. For the chlorobenzenes considered, experimental values for humic acid agreed most closely with those from soil, although triolein and lignin were also similar. Theoretical partition coefficients were in general lower than experimental values, but within a factor of 10 . Closest agreement was noted with triolein. Soil/water partition coefficients were consistent with partitioning between humic acid and water.     

热带滨海区不同土地利用背景下土壤溶解性有机氮的组成与粒径分布特征

溶解态有机氮(DON)是土壤中活跃的氮库,其生态环境行为与它的化学组成和粒径分布密切相关。为评估热带滨海区不同土地利用方式对不同粒径中土壤溶解性有机氮组成特征的影响,从水稻田、橡胶园、菜园和果园采集土壤样品,通过一系列微滤和超滤(0.7,0.45,0.2,0.1μm,100,10,1 kDa)对土壤溶解性有机氮分级,并使用连续流动分析仪、三维荧光光谱和红外光谱研究了滤液中溶解态有机氮、无机氮的含量及荧光组分和有机官能团特征。结果表明,4种土地利用背景下土壤DON值的范围为5.25-10.88 mg·kg^-1,其大小顺序为水稻>菜园>果树>橡胶,且DON与溶解性总氮(DTN)的比值范围为26.08%-67.11%,其中橡胶土最高,水稻土最低;不同粒径下4种土地利用类型土壤DON主要集中在<100 kDa的粒径中,其值范围为4.85-9.48 mg·kg^-1,占全量的85.89%-92.41%。三维荧光光谱(3D-EEMs)及平行因子分析表明,4种土地利用背景下土壤DON含有两种类腐殖质组分及一种类蛋白质组分,且以类腐殖质组分为主,占比54.00%-77.67%;类蛋白组分对土地利用变化敏感,且随着粒径的减小,类蛋白组分占比增加,在<1 kDa组分中比例最高。红外光谱结果表明,4种土地利用背景下土壤DON主要在6个位置有相似的吸收峰,包含3410 cm^-1、1636 cm^-1、1402 cm^-1、1138-1035 cm^-1、673 cm^-1、602 cm^-1,不同土地利用背景下各吸收峰的透光度不同,强度最大的吸收来自游离的胺类N-H伸缩振动;水稻、菜园土壤DON芳香物质含量较高,结构较复杂。了解DON的组成与粒径分布对土地利用的响应,对进一步研究其生态环境行为具有重要意义。     

Characterization of dissolved organic carbon and Humic substances in the well water of the Blackfoot disease area in Taiwan

Since the early 1960s, many investigators have reported that blackfoot disease, a peripheral vascular disease, observed in southwestern Taiwan is due to drinking the higher arsenic concentration in well water. However, recent studies indicated that the relationship with blackfoot disease is not only with arsenic but also humic substances. This paper presents some results concerning the characterization (such as fluorescence, elemental composition, molecular weight and carbon distribution) of humic substances isolated from the Fuhsing well water of the blackfoot disease area. For comparison, the dissolved organic carbon (DOC) and humic substances in the normal well water from Chiuying and the Nanwan coastal water were also analyzed. In general, in the well water of the blackfoot disease area, extremely high concentrations of DOC (18.5mg/L) and fulvic acid (7.54mg/L) with high fluorescence intensity (59.1, equivalent to 0.0282uM quinine sulfate solution) and high percentages (over 50%) of low molecular weights of less than 1,000 were obtained compared with those of normal waters. C‐13 Nuclear magnetic resonance spectroscopy showed a high content (37.2%) of aromatic carbon. These higher concentrations of DOC and fulvic acid with the higher content of aromatic carbon in well water might be one of the key factors causing the blackfoot disease in Taiwan.     

Characterization of humic substances in bio-treated municipal solid waste landfill leachate

Considerable organic matter remains in municipal solid waste landfill leachate after biological treatments. Humic substances (HSs) dominate the organic matter in bio-treated landfill leachate. In this study, the HSs from landfill leachate treated by membrane bioreactor (MBR-HSs) were analyzed via elemental analysis, ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, and charge polarized magic-angle spinning-¹³C-nuclear magnetic resonance. The characteristic absorption in the UV wavelength range indicated the presence of high C=C and C=O double bonds within the MBR-HSs. Compared with commercial HSs, MBR-HSs had lower carbon content [48.14% for fulvic acids (FA) and 49.52% for humic acids (HA)], higher nitrogen content (4.31% for FA and 6.16% for HA), lower aromatic structure content, and higher carbohydrate and carboxylic atoms of carbon content. FA predominantly had an aliphatic structure, and HA had less condensed or substituted aromatic ring structures than natural HA. The aromatic carbon content of MBR-HSs was lower than that of humus-derived HSs but higher than that of waste-derived HSs, indicating that MBR-HSs appeared to be more similar to humus-derived HSs than waste-derived HA.     

Phototransformation of <Emphasis Type="SmallCaps">l</Emphasis>-tryptophan and formation of humic substances in water

Humic substances are poorly known, though they represent a major pool of non-biotic organic carbon on earth. In particular, there is little knowledge on the formation of humic substances by irradiation of organic matter dissolved in waters. Specifically, it is known that humic substances can be formed from proteins by photochemical processes in surface waters, but the role of single amino acids and their transformation pathways are not yet known. Therefore, here we studied the phototransformation of aqueous l-tryptophan under simulated sunlight. Irradiated l-tryptophan solutions were analyzed by absorption, fluorescence, nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies, chromatography, potentiometry and mass spectrometry (MS). The solutions appeared turbid after irradiation; therefore, nephelometry and dynamic laser light scattering were used to characterize the suspended particles. Results show that about 95% of l-tryptophan was degraded in 8-h irradiation, undergoing deamination and decarboxylation of the amino acidic moieties to release ammonium and formate. The MS signal at m/z 146 suggests the formation of 3-ethylindole, while pH-metric and NMR data revealed the presence of hydroxylated compounds. The phototransformation intermediates of l-tryptophan had fluorescence and absorption spectra similar to those of humic substances, they were able to produce ^·OH upon irradiation and tended to aggregate by both ionic and hydrophobic interactions. Overall, our findings reveal for the first time the nature of products formed upon phototransformation of l-tryptophan. Interestingly, the transformation of l-tryptophan is quite different from that of the previously studied l-tyrosine, although both compounds produce humic-like materials under irradiation.     

长江重庆段溶解性有机物的荧光特性分析

利用三维荧光光谱(EEMs),并结合平行因子分析(PARAFAC)及主成分分析(PCA),研究了长江重庆段溶解有机物(DOM)的荧光组分特征及其污染来源,并探讨了荧光强度同溶解性有机碳(DOC)及溶解氧(DO)的相关性.结果表明,PARAFAC模型识别出长江重庆段DOM由2类6个荧光组分组成,即类腐殖质荧光组分C1(350/422 nm)、C4(245,305/395 nm)、C5(260,340/420 nm)、C6(260/480 nm)及类蛋白荧光组分C2(275/300 nm)、C3(227,278/329 nm).在DOM来源组成中,陆源的类腐殖质含量占62.56%,类蛋白物质含量占31.31%.类腐殖质组分的荧光强度同DOC的含量存在明显的线性正相关(r=0.73),类蛋白组分的荧光强度同DO的含量呈明显的线性负相关(r=0.80).EEMs-PARAFAC不仅可以表征长江重庆段DOM的光谱特征,示踪长江重庆段的有机污染程度,还可以为三峡库区水体保护提供依据.     

Effects of humic acid fractions with different polarities on photodegradation of 2,4-D in aqueous environments

Four fractions (A, B, C, and D) of humic acids (HAs) were separated based on the polarity from weak to strong. UV-vis absorption and Fourier transform infrared spectroscopy (FTIR) analysis show that the fractions C and Dpossessedmore aromatic C=C content. The influences of HAs and their fractions on the photolysis were investigated by the photodegradation of 2,4-D solutions under simulated solar light irradiation. The degradation rate of 2,4-D was found to decrease in the presence of bulk HAs or their fractions especially at high HAs concentration. The fractions of strong polarity C and D retarded the degradation rate more than the fractions of weak polarity A and B. This could be attributed to the different absorption intensity of the four HAs fractions in the order of D ? C > A > B, and the stronger π-π electron donor-acceptor interactions between the strong polar fractions and 2,4-D.